2026 · Journal of the American Chemical Society
Catalytic Asymmetric Diels–Alder Reaction of β,β-Disubstituted Enals with Cyclopentadiene: Syntheses of (−)-Camphene, (−)-β-Santalene, and (−)-( Z )-β-Santalol ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract Despite the long and rich history of the Diels–Alder reaction, certain aspects of its scope still remain remarkably underexplored. Most prominently, reactions with β,β-disubstituted enals as dienophiles are scarcely represented in the literature. The first general and highly enantioselective method, enabled by a strongly acidic and confined imidodiphosphorimidate organocatalyst, is reported here. The reaction tolerates a broad range of enals, including substrates with functional groups and complex alkenyl substituents, delivering the corresponding cycloadducts in good yields and excellent enantioselectivity. The synthetic utility of the method is further highlighted by concise asymmetric total syntheses of (−)-camphene, (−)-β-santalene, and (−)-(Z)-β-santalol from inexpensive starting materials.
2026 · Journal of the American Chemical Society
The Catalytic Asymmetric Alkylation of Olefins with Alcohol Derivatives ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
Both olefins and arenes are abundant and versatile feedstock chemicals. Although the electrophilic alkylation of arenes constitutes an advanced technology, the corresponding alkylation of olefins is rather undeveloped. Here, we report an asymmetric catalytic benzylation and allylation of unactivated olefins with acetates as electrophiles. The reaction is catalyzed by a single imidodiphosphorimidate organocatalyst operating as a silylium Lewis acid. Mechanistic experiments support an enantioconvergent SN1 mechanism featuring stereoablative ion pair formation, resulting in a dynamic kinetic resolution. The enantioenriched hydrocarbon products are readily derivatized to odorants and nonsteroidal anti-inflammatory drugs in one or two steps. The developed method provides a metal-free alternative to cornerstone Tsuji-Trost-type allylations proceeding though π-allyl metal complexes.
2026 · Nature Catalysis
Catalytic asymmetric intermolecular carbonyl–ene-type reactions of unactivated aldehydes and alkenes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract Carbonyl–ene-type reactions are recognized by chemists for their ability to form carbon–carbon bonds between aldehydes and alkenes, both abundantly available early-stage chemicals. However, despite remarkable progress with intramolecular variants, intermolecular carbonyl–ene-type reactions in which unactivated aldehydes react with unactivated alkenes are underexplored and, to the best of our knowledge, catalytic enantioselective versions have not yet been described. Here we report a solution to this problem that enables a variety of unactivated aromatic and aliphatic aldehydes to be united with alkenes, furnishing highly enantioenriched homoallylic alcohols. The method benefits from the high reactivity of confined silylium ion-based organic Lewis acid catalysts, which, according to computational studies, mediate a cationic Prins-type pathway.
2026 · Synfacts · editorial
Hydrogen-Bond-Gated PCET Enables Intermolecular Alkoxy Radical Hydroetherification ↗Radical Photochemical Reactions
Abstract
Keywords hydroetherification - alkoxy radicals - proton-coupled electron transfer Publication History Article published online: 29 July 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric [4+2] Photocycloaddition of Aminoquinolines with Styrenes to Tetrahydroquinolines ↗Radical Photochemical Reactions
Abstract
Keywords [4+2] photocycloaddition - aminoquinolines - tetrahydroquinolines - Brønsted acid catalysis Publication History Article published online: 29 July 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Outer-Sphere Photometallobiocatalytic Radical C–C Cross-Coupling ↗Radical Photochemical Reactions
Abstract
Keywords photometallobiocatalysis - outer-sphere mechanism - iron carbenoids - radical C–C coupling - metalloenzyme Publication History Article published online: 29 July 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
A Relay Energy Transfer Strategy for Asymmetric Photocatalysis ↗Radical Photochemical Reactions
Abstract
Keywords p-chiral - dearomative [4+2] cycloaddition - relay catalysis Publication History Article published online: 29 July 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Journal of the American Chemical Society
Catalytic Asymmetric Cationic Geranyl Cyclizations ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
Cyclogeranyl motifs are important in natural products and terpene synthesis, yet their asymmetric formation from acyclic dienes remains challenging. Here, we report a general catalytic asymmetric cyclization of geranyl derivatives using confined chiral imidodiphosphorimidate (IDPi) Brønsted acids. In combination with fluorinated alcohol additives, the reaction proceeds under mild conditions with high efficiency and excellent regio- and enantioselectivity. The method accommodates diverse substrates, enabling access to fragrance-relevant scaffolds, retinal precursors, complex polycyclic terpenes, and even selective squalene cyclization. Mechanistic studies support a cooperative catalyst-additive hydrogen-bonding network and an asynchronous concerted, enzyme-like transition state within a confined chiral environment. This work provides a general solution for asymmetric geranyl cyclizations and expands the utility of confined Brønsted acid catalysis in biomimetic terpene synthesis.
2026 · Synfacts · editorial
Enzymatic Nitrile Oxide Formation and Subsequent [3+2] Cycloaddition with Alkenes to Access Isoxazolines ↗Vanadium and Halogenation Chemistry
Abstract
Keywords isoxazolines - oxidative [3+2] cycloaddition - vanadium-dependent haloperoxidase Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Stereodivergent Inverse-Electron-Demand Diels–Alder Reactions via Prolinol-Type Catalysts ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Keywords enantiocontrol - asymmetric catalysis - Diels–Alder reaction - stereodivergent - prolinol-type catalysts Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photobiocatalytic Enantioselective C(sp3)–C(sp3) Coupling through Thiamine-Dependent Radical Catalysis ↗Radical Photochemical Reactions
Abstract
Keywords photobiocatalysis - radical coupling - C(sp 3 )–C(sp 3 ) bond formation - thiamine-dependent enzymes - photoredox catalysis Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Amide Synthesis Using Thioacids and Anilines via EDA Photoactivation ↗Radical Photochemical Reactions
Abstract
Keywords EDA photoactivation - tetrachlorophthalimide - amide synthesis - thioacids - anilines Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photocatalytic Platform for Alkyl-to-Aryl Nitrogen Translocation ↗Radical Photochemical Reactions
Abstract
Keywords nitrogen migration - benzolactam - C(sp 3 )-to-C(sp 3 ) - radicals Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Highly β-Selective O-Glycosylation ↗Carbohydrate Chemistry and Synthesis
Abstract
Keywords α-glycosyl donors - β-glycosylation - S N 1-like pathway - IDPi - acid catalysis Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Organocatalytic Elimination of Cyclobutanols ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords asymmetric concerted elimination - desymmetrization of cyclobutanol - E2-type mechanism Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Biocatalysis Enables Efficient Access to a Mosquito Repellent ↗Plant biochemistry and biosynthesis
Abstract
Keywords squalene-hopene cyclases (SHCs) - Prins cyclization Publication History Article published online: 25 June 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Journal of the American Chemical Society
Catalytic Asymmetric Hydration of Alkenes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
The asymmetric Markovnikov hydration of alkenes to alcohols, transforming abundant feedstock chemicals and water into synthetically versatile building blocks, has long remained inaccessible. The reaction is inherently reversible because of unfavorable entropy, preventing asymmetric induction. While lowering the temperature should favor product formation in principle, such conditions are normally incompatible with the required protonation of simple alkenes and with maintaining a homogeneous reaction mixture. Here we show that this long-standing limitation is overcome by making catalytic activity viable under cryogenic conditions. Using confined strong Bro̷nsted acid catalysts and solvent-organized hydrogen-bonding networks that facilitate protonation of otherwise unreactive alkenes, we achieve a highly enantioselective hydration of electronically neutral alkenes with water. This thermodynamic temperature dependence also allows conversion of racemic tertiary alcohols into enantioenriched forms through a one-pot formal deracemization. Experimental and computational studies indicate that perfluorinated solvents form extended hydrogen-bonding networks that enhance both reactivity and stereocontrol. These findings establish a general strategy for overcoming fundamental constraints imposed by reversibility.
2026 · Synfacts · editorial
Organocatalytic Asymmetric Enantioselective Synthesis of Nucleoside Analogues ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords aldehyde - α-fluorination - aldol reaction - imidazolidinone catalyst - L -proline - RAvIN ketone - nucleoside analogue synthesis - enamine catalysis Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photocatalyzed Aryl-Substituent Dance on Pyridines ↗Radical Photochemical Reactions
Abstract
Keywords pyridines - transposition - photochemistry - meta -substitution Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
A Peptide-Catalyzed Fluorination Using CsF ↗Fluorine in Organic Chemistry
Abstract
Keywords peptidic catalysis - phase-transfer catalysis - asymmetric fluorination - fluorinase - metal fluorides Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Oxoammonium-Catalyzed Enantioselective Hydride Transfer Enables Desymmetrization of meso-Pyrrolidines ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords enantiocontrol - asymmetric catalysis - oxoammonium - desymmetrization - hydride transfer Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Enantiodivergent Isomerization of Alkynoates to Axially Chiral Allenoates ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Keywords chiral allenoates - axial chirality - stereoselective 1,3-proton transfer - enantiodivergence - flavin-dependent “ene”-reductase - directed evolution Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Organocatalytic meta-C–H Thiolation of Quinolines ↗Sulfur-Based Synthesis Techniques
Abstract
Keywords azaarenes - [3,3]-sigmatropic rearrangement - dearomative thiolation Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Activation of Oxetanes for Heteronuclear Dual-Atom Insertion ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Keywords skeletal editing of oxetanes - borane catalysis - 1,3-oxazinanes Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Peptide-Catalyzed Stereoselective Michael Addition for Head-to-Tail Macrocyclization ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords peptide catalysis - head-to-tail macrocyclization - Michael addition - enamine activation Publication History Article published online: 27 May 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Angewandte Chemie
Structure–Selectivity Relationship Study of IDPi Using Fragment and Remote Site Descriptors ↗Asymmetric Synthesis and Catalysis
Abstract
ABSTRACT Imidodiphosphorimidate (IDPi) has emerged as a powerful chiral organocatalyst featuring a specially designed cavity constructed by aryl group‐substituted BINOL units. Despite extensive applications of IDPi in asymmetric reactions, the understanding of its structure–selectivity relationship (SSR) remains underdeveloped. In this study, we employed aryl fragment descriptors for the statistical modeling of IDPi‐catalyzed asymmetric reactions, offering a cost‐effective and efficient approach to explore the SSR of IDPi. Specifically, site parameters of remote sp 2 carbon atoms were defined to capture the features of the distal ring of the aryl substituents. The established statistical models of IDPi‐catalyzed cyanosilylation reactions align well with the mechanistic understandings of the crucial role of C‐H···π and cation‐π interactions between the distal ring of IDPi and substrate in stereo‐control. More selective catalysts for the challenging cyanosilylation reaction of 3‐hexanone were successfully identified by using these descriptors to define and screen the chemical space of IDPi catalysts. This work not only enriches our understanding of the SSR of IDPi catalysts but also highlights the potential application of aryl fragment and remote site parameters as universal descriptors for IDPi in statistical modeling.
2026 · Journal of the American Chemical Society
Confined Acids Catalyze a Broadly Applicable β-Selective O -Glycosylation ↗Open accessCarbohydrate Chemistry and Synthesis
Abstract
Glycans are fundamental components of biological systems, composed of monosaccharides linked through glycosidic bonds. The stereogenic nature of these glycosidic bonds plays a decisive role in the structure and biological function of the glycan. Achieving precise, stereocontrolled formation of glycosidic linkages has therefore been a long-standing objective and an ongoing challenge for chemists. To date, general catalytic β-selective glycosylations have been limited to S N 2-like reactions with competing S N 1-like pathways via oxocarbenium ions eroding the selectivity. Here we report an alternative approach: confined acids catalyze a broadly applicable β-selective O -glycosylation, including 2-deoxyglucosylation, glucosylation, and mannosylation, that we suggest proceeds via an S N 1-like pathway. Mechanistic and theoretical studies support this view.
2026 · ACS Central Science
Predicting Enantioselectivity via Kinetic Simulations on Gigantic Reaction Path Networks ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Asymmetric catalysts exert control over the reactivity and enantioselectivity of chemical reactions, often through their large size and highly flexible geometries. Current quantum chemical calculations provide a powerful means to predict enantioselectivity through exhaustive conformational sampling at the selectivity-determining transition state (TS). However, this approach still relies on a predetermined selectivity-determining step and on the assumption that selectivity is governed by the Boltzmann distribution of TS conformers. To address this issue, constructing a reaction path network that captures the kinetically accessible regions of the potential energy surface is essential. In this study, we applied a delta-learning neural network potential (ΔNNP) to an asymmetric organocatalyst belonging to the imidodiphosphorimidates (IDPi) family, comprising over 200 atoms. The ΔNNP demonstrated accuracy comparable to that of density functional theory (DFT) using GFN2-xTB as the baseline method and learning the DFT–GFN2-xTB energy differences through the neural network model. Using the ΔNNP-based single component - artificial force induced reaction (denoted by NNP/AFIR) method, we constructed a reaction path network containing 48463 paths. Kinetic simulations based on this network were then performed to predict the reaction mechanism and enantioselectivity. Within the network, neumerous paths, including asynchronous concerted and stepwise mechanisms, were found to be energetically competitive and thus to contribute to the overall kinetics. Traffic volume analysis further revealed that intermediates with negligible yields can still play important kinetic roles. Overall, the NNP/AFIR approach would provide a powerful framework not only for deepening mechanistic understanding but also for accelerating the rational design of asymmetric catalytic systems with high reactivity and enantioselectivity.
2026 · Synfacts · editorial
Nitrosonium-Ion-Catalyzed Oxidative Chlorination of Arenes Using Environmentally Friendly Reagents ↗Oxidative Organic Chemistry Reactions
Abstract
Keywords oxidative chlorination - nitrosonium ions - chloroarenes - sustainable chemistry Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Birch Reduction of Electron-Rich Arenes under Mild Conditions Enabled by Photocatalysis ↗Radical Photochemical Reactions
Abstract
Keywords organophotocatalysis - Birch reduction - spirocycle synthesis - dearomatization Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Carbonium Ion Catalysis: IDPi-Catalyzed Hydroalkoxylation of Cyclopropanes ↗Cyclopropane Reaction Mechanisms
Abstract
Keywords carbonium ion catalysis - intramolecular hydroalkoxylation - cyclopropanes - asynchronous concerted mechanism Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Enantioselective [1,2]-Wittig Rearrangement by Combining [2,3]- and [1,3]-Sigmatropic Rearrangement ↗Phosphorus compounds and reactions
Abstract
Keywords allylic ethers - [1,2]-Wittig rearrangement - sigmatropic rearrangement - bifunctional iminophosphorane - base catalysis Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photocoupling N-Heteroarenes and Unprotected Sugars ↗Radical Photochemical Reactions
Abstract
Keywords EDA complex - photocatalysis - sugars - N-heteroarenes Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Catalytic Asymmetric Synthesis of 1,1-Disubstituted Isochromans ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords enantiocontrol - asymmetric catalysis - isochromans - CBSCA catalyst - β-aryl ethanols Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
The Uphill Photohydrolysis of Furans and Furfurals ↗Free to readFree PDF ↗Radical Photochemical Reactions Abstract
Keywords furan derivatives - succinaldehyde - 1,4-ketoaldehydes - 1,6-dioxecine - redox-neutral - endergonic - photocatalysis Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photoredox Deaminative Benzylic Functionalization via 1,4-Dihydropyridine-Mediated C–N Bond Activation ↗Radical Photochemical Reactions
Abstract
Keywords 1,4-dihydropyridines - photoredox catalysis - benzylic functionalization Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Synthesis of β-Sultams via Visible-Light Energy-Transfer Catalysis ↗Radical Photochemical Reactions
Abstract
Keywords β-sultams - energy transfer - photocycloaddition - sulfinylamines - strained heterocycles Publication History Article published online: 26 March 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Construction of Chiral Spirobarbiturates Involving an Organocatalytic Proton Shuttle ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords asymmetric organocatalysis - spirobarbiturates - hydrogen-bond donor Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
A Simple Prolyl Amide as Organocatalyst in the Enantioselective Pictet–Spengler Reaction ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords α-diketones - Pictet–Spengler reaction - single H-bond donor - tetrahydro-β-carboline Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Organocatalytic Construction of P(V) Stereogenic Centers: Methylation and Beyond ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords asymmetric alkylation - P-stereogenic compounds - organocatalysis - phase-transfer catalyst - heteroatom stereogenicity Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
An Approach to Energy Transfer Using Widely Available Nitroarenes as Photocatalysts ↗Radical Photochemical Reactions
Abstract
Keywords nitroarenes - photocatalysis - E -to- Z alkene isomerization - [2+2] cycloaddition Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Spin-Center Shift Allows Ring-Expansion of Cyclic Carboxylic Acids ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords ring expansion - spin-center shift - carboxylic acids Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Development of the New-to-Nature Nonheme Fe Biocatalysts for Synthesis of Arylglycines ↗Metal-Catalyzed Oxygenation Mechanisms
Abstract
Keywords nonheme Fe-enzymes - nitrogen migration - isopenicillin N synthase - arylglycines Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Synthesis of Mechanically Planar Chiral Rotaxanes via Enantioselective Povarov Reactions ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords asymmetric catalysis - asymmetric Povarov reaction - chiral phosphoric acids - enantioselective desymmetrization - rotaxanes Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Visible-Light-Driven Deracemization of Amino Alcohols via Chiral HAT Catalysis ↗Radical Photochemical Reactions
Abstract
Keywords deracemization - chiral HAT - cinchona alkaloids - amino alcohols Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Silylium-IDPi Lewis Acid Catalyzed Asymmetric Synthesis of Acyclic N-Stereogenic Amines ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Keywords N-stereogenic amines - anomeric amines - Brønsted acid catalysis - silyl ketene acetals - enantiolobal differentiation Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Catalytic Asymmetric Carbosilylation of Methyl Propiolate ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords enantiocontrol - asymmetric catalysis - carbosilylation - bis-silyl ketene acetals - methyl propiolate Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Photoenzymatic Synthesis of γ-Stereogenic Nitriles ↗Enzyme Catalysis and Immobilization
Abstract
Keywords photoenzymatic - flavoproteins - ene-reductase - nitiriles - alkenes - enantioselective Publication History Article published online: 25 February 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Journal of the American Chemical Society
The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with Cyclic Enones: Short Routes to Jasmonates ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
A silylium imidodiphosphorimidate (IDPi) Lewis acid catalyst enables a broadly applicable organocatalytic asymmetric Mukaiyama-Michael addition of moderately electrophilic cycloenones with enol silanes, affording 1,4-adducts in up to 98% yield and >99:1 e.r. At 0.05 mol % catalyst loading, the reaction scales to 167 g of product with 96% catalyst recovery. The method accommodates a wide range of enones and silylated nucleophiles, allowing streamlined access to key jasmonates and related valuable targets. Computational studies elucidated the origin of the enantioselectivity in this reaction. This platform thus provides a versatile entry to structurally complex chiral scaffolds with direct relevance to plant signaling, fragrance chemistry, aromatherapy, and pharmaceutical sciences.
2026 · Chinese Journal of Chemistry
Acid‐Catalyzed Synthesis of Si ‐Stereogenic Silanes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Comprehensive Summary The importance of Si ‐stereogenic silanes has been recognized in many fields of chemical science. Consequently, numerous catalytic enantioselective methods for their synthesis have been developed. Despite these advances, such methods have traditionally relied on transition‐metal catalysts, predominantly rhodium and palladium. Recently, Brønsted acid catalysts have emerged as powerful alternatives to transition‐metal catalysts. In particular, imidodiphosphorimidate (IDPi) and chiral phosphoric acid (CPA) catalysts have enabled access to structurally diverse Si ‐stereogenic silanes, including silyl ethers, silacycles, and disiloxanes, that were not previously attainable. In this review, we describe the recent advances made in Brønsted acid catalysis for the synthesis of Si ‐stereogenic silanes. We also discuss the relevant background and reaction mechanisms. We hope that this review will suggest future research directions in this emerging area. Key Scientists
2026 · Synfacts · editorial
Asymmetric Azidation of Enedials through N-Heterocyclic Carbene Catalysis ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Keywords NHC catalysis - azidation - Breslow intermediate Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Electricity-Driven Lewis Base Catalyzed Stereoselective α-Functionalization of Esters ↗Asymmetric Synthesis and Catalysis
Abstract
Keywords isothiourea catalysis - electrochemical catalysis - α-functionalization Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
An Unprecedented Diels–Alder Reaction with α,β- and β,β-Disubstituted Enones ↗Organic Chemistry Cycloaddition Reactions
Abstract
Keywords Diels–Alder reaction - disubstituted enones - IDPi catalysis - fragrance synthesis Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · The Cambridge Structural Database · dataset
CCDC 2490190: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2026 · Synfacts · editorial
Enzymatic Stereocontrolled De Novo Cyclopropanation Enabled by a Multifunctional Class I Aldolase ↗Cyclopropane Reaction Mechanisms
Abstract
Keywords enantiocontrol - asymmetric catalysis - NahE variants - cyclopropanes - aldolase Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Accessing Axially Chiral Sulfoxides ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Keywords 3-(aryl)-1-naphthols - sulfinylation - stereogenic sulfur(IV) - axial chirality - squaramides - hydrogen-bonding catalysis Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Biocatalytic Stereoselective Hydroamination of Olefins Enabled by a Biotin-Based Thiophenol Cofactor ↗Enzyme Catalysis and Immobilization
Abstract
Keywords asymmetric hydrogen atom transferases - artificial cofactors - hydroamination Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Synthesis of α-Amino Acids via ConPET-Driven Amide Activation ↗Free to readFree PDF ↗Carbon dioxide utilization in catalysis Abstract
Keywords ConPET - CO 2 fixation - α-amino acids - isotopic labeling - amides Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Synergistic Photobiocatalytic Radical Repositioning for Remote Enantioselective Acylation ↗Enzyme Catalysis and Immobilization
Abstract
Keywords photobiocatalysis - thiamine-dependent enzymes - NHC catalysis - remote C–C/C–H bond functionalization Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Synfacts · editorial
Asymmetric Hydrogen Atom Transfer from Cofactors to Unactivated Olefins via Enzyme Catalysis ↗Enzyme Catalysis and Immobilization
Abstract
Keywords asymmetric transfer hydrogenation - unactivated styrenes - enzymatic reduction Publication History Article published online: 28 January 2026 © 2026. Thieme. All rights reserved. Georg Thieme Verlag KG Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
2026 · Science
The photohydrolysis of furans ↗Open accessCatalysis for Biomass Conversion
Abstract
The defossilization of the chemical industry is accelerated by the shift from petroleum- to biomass-based feedstocks. At the center stage are bioderived furans, from which valuable platform chemicals can be obtained exclusively through oxidative or reductive processes. By contrast, the conceptually straightforward redox-neutral hydrolysis of furan to succinaldehyde and 2-substituted furans to 1,4-ketoaldehydes has been considered unfeasible owing to their endergonicity and polymerization side reactivity. In this work, we report the realization of this uphill furan hydrolysis through photocatalysis involving a highly strained, 10-membered 1,6-dioxecine intermediate. Succinaldehyde, as well as 1,4-ketoaldehydes, can be directly obtained from furans. Additionally, furfural derivatives undergo redox-enhanced Piancatelli rearrangements, accessing antimicrobial natural products (±)-Terrein and (±)- epi -Pentenomycins. The methodology was applied to the redox-neutral production of common industrial fine chemicals, avoiding wasteful redox detours typical in biomass-based synthesis.
2026 · Nature Synthesis
Catalytic asymmetric activation of bicyclobutanes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge for chemical synthesis and catalysis. Stereodifferentiation in strained alkanes is particularly difficult to accomplish because a catalyst has to distinguish various highly exergonic chemo- and stereoselective strain-release channels. Here we disclose an organocatalytic asymmetric hydroalkoxylation of bicyclobutanes with alcohols to efficiently access tertiary cyclopropylcarbinyl ethers with high enantioselectivity (e.r. up to 98:2). Enantiocontrol is accomplished through chiral recognition between the confined iminoimidodiphosphoric acid catalyst and the substrate, mediated by non-covalent interactions between a Lewis basic binding site of the confined anion and the polarized C–H bond of the cyclopropylcarbinyl ion intermediate. Our work establishes bicyclobutane activation by harnessing strain-release energetics while maintaining precise stereo- and regiocontrol through structural confinement.
2026 · Journal of the American Chemical Society
Asymmetric Carbonium Ion Catalysis: The Intramolecular Hydroalkoxylation of Cyclopropanes ↗Open accessFree PDF ↗Cyclopropane Reaction Mechanisms Abstract
Cyclopropanes serve as valuable synthetic intermediates in drug discovery and natural product synthesis. However, the stereoselective functionalization of cyclopropanes remains a fundamental challenge, traditionally necessitating the prior activation of the parent hydrocarbon. Here, we report an organocatalytic asymmetric intramolecular hydroalkoxylation of cyclopropanes that overcomes this constraint using chiral imidodiphosphorimidate catalysts. Our strategy directly affords enantioenriched substituted tetrahydrofurans with high enantioselectivity (up to 96.5:3.5 er). Kinetic analyses reveal a zero-order dependence on the substrate and support catalyst saturation. Combined experimental and computational studies suggest that the prereaction catalyst-substrate ion pair is stabilized through noncovalent interactions leading to the formation of a transient cycloproponium ion-like transition state. This work provides a potentially general platform for stereoselective cyclopropane functionalization.
2025 · Journal of the American Chemical Society
Catalytic Asymmetric Carbosilylation of Methyl Propiolate with Bis-silyl Ketene Acetals ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
We report a catalytic asymmetric silylative α-alkenylation of bis-silyl ketene acetals (bis-SKAs) with methyl propiolate via conjugate addition. In contrast to prior Brønsted-base activation of C-H acidic nucleophiles (β-ketoesters and oxazolones), electrophilic activation of the alkynoate through silylium-asymmetric counteranion-directed catalysis (Si-ACDC) enables this transformation. DFT studies support a pathway in which silylium-mediated addition forms a substituted alkoxy(trimethylsilyloxy)propadiene (silyl propadienone acetal, SPA) that rapidly isomerizes via C-silylation accompanied by an O-desilylation to the α,β-unsaturated α-silyl ester with high stereocontrol. The reaction shows a broad scope with uniformly excellent enantio- and diastereoselectivities, and we demonstrate several downstream modifications of the products.
2025 · MPG.PuRe (Max Planck Society)
IDPi Catalysis: Revolutionizing Asymmetric Synthesis ↗Free copyFree PDF ↗Asymmetric Synthesis and Catalysis 2025 · Nature
The asymmetric synthesis of an acyclic N-stereogenic amine ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
Abstract Most molecules in chemistry and biology are chiral, leading to mirror-image variants, so-called enantiomers. However, although the selective chemical synthesis of molecules in which the stereogenicity arises from a carbon atom is well-established, enantioselective approaches to nitrogen-stereogenic molecules are much less common 1–3 , and in case of acyclic, N -stereogenic amines, even unknown, because of their rapid pyramidal inversion. Here we describe the catalytic asymmetric synthesis of stable, acyclic N -stereogenic amines by the addition of enol silanes to nitronium ions that ion pair to a confined chiral anion. In the produced so-called anomeric amines, the commonly observed isomerization is slowed down by two N -oxy-substituents, which hamper nitrogen inversion. The important stereogenicity-creating step challenges previously established stereochemical descriptors of enantiodifferentiation. Computational studies provide further insight into the origin of the observed stereocontrol. Our work opens up a new avenue to investigate the fascinating and previously underexplored chemistry of enantiopure anomeric amines.
2025 · Journal of the American Chemical Society
Catalytic Enantioselective Diels–Alder Reaction of Dienes with Acyclic and α,β- and β,β-Disubstituted Enones ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Despite the wealth of methods to enantioselectively catalyze Diels-Alder reactions of α,β-unsaturated carbonyl dienophiles, until today, not a single example with an acyclic enone that is either β,β- or α,β-disubstituted has been reported. Herein, we disclose a general Brønsted acid-catalyzed enantioselective Diels-Alder reaction of various aliphatic acyclic disubstituted enones with hydrocarbon dienes featuring diverse steric and electronic properties. The established method has been employed to synthesize several enantiopure targets, including well-known fragrance components such as arborone and the damascones.
2025 · Journal of the American Chemical Society
Catalytic Asymmetric ( ene – endo )-Carbonyl–Ene Type Cyclizations ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide The carbonyl–ene reaction between aldehydes and olefins constitutes a perfectly atom economic approach to homoallylic alcohols with concomitant C–C bond formation. However, the scope of catalytic asymmetric intermolecular versions is currently limited to activated substrates, while of the two intramolecular types only catalytic asymmetric ( ene – exo )-carbonyl–ene type cyclizations can be considered mature. The corresponding ( ene – endo )-cyclizations would arguably find equal utility in chemical synthesis but remain underdeveloped. Herein, we report an efficient regio- and enantioselective catalytic asymmetric ( ene – endo )-carbonyl–ene type cyclization of unbiased alkenyl aldehydes using a strong and confined IDPi Brønsted acid catalyst. High enantioselectivities of up to 98:2 e.r. were obtained for a range of homoallylic alcohols.
2025 · Journal of the American Chemical Society
Catalytic Asymmetric Ionic Hydrogenation of α-Alkyl Styrenes ↗Open accessFree PDF ↗Asymmetric Hydrogenation and Catalysis Abstract
Over the past two decades, chemists have made significant advances in the field of catalytic asymmetric transfer hydrogenation of various unsaturated compounds with biomimetic hydrogen donors. The reduction of carbon-carbon double bonds, however, has been limited to activated substrate classes, such as enals, enones, nitroolefins, or α-(2-hydroxyaryl) styrenes. Here we report a highly enantioselective Brønsted acid-catalyzed ionic hydrogenation of α-alkyl styrenes using a hydrosilane in combination with a protic additive. Mechanistic and computational investigations support a pathway proceeding through a carbocation intermediate and a transient silylated catalyst species, with catalyst turnover dependent on the presence of a protic additive. Moreover, the exemplary stereoconvergent reduction of a trisubstituted alkene highlights the potential of organocatalytic approaches over traditional metal-catalyzed hydrogenations.
2025 · Synthesis
Asymmetric Prins Cyclizations of O-Prenylated Salicylaldehydes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract We report the asymmetric intramolecular Prins cyclization reactions of O-prenylated salicylaldehydes to 4-chromanols. Excellent efficiencies and selectivities were herein obtained using a highly fluorinated imino-imidodiphosphate (iIDP) Brønsted acid catalyst. The presented method tolerates substrates bearing both electron-donating and electron-withdrawing groups.
2025 · Journal of the American Chemical Society
The Overlooked Stereoisomers of the Ionizable Lipid ALC315 ↗Open accessFree PDF ↗RNA Interference and Gene Delivery Abstract
Lipid nanoparticles (LNPs) are a powerful delivery platform for nucleic acid therapeutics such as mRNA vaccines and gene therapies. Central to their success are ionizable lipids, which facilitate the cellular uptake and endosomal escape of nucleic acids. However, achieving a high delivery efficiency often comes with the drawback of increased cytotoxicity. Here, we report a chemical, biological, and toxicological investigation into the three stereoisomers of ALC315, a mixture of which constitutes one of the most successful marketed ionizable lipids for LNPs. We demonstrate that the individual stereoisomers of ALC315 can be accessed by either the asymmetric chemical synthesis or chromatography of an intermediate. An LNP formulation based on a single stereoisomer of ALC315 enhances mRNA transfer efficiency while reducing the associated cytotoxicity in human cell lines. Our results underscore the potential of stereochemically pure ionizable lipids as key components in the development of next-generation nucleic acid therapies, offering an enhanced delivery performance and better safety profiles.
2025 · ACS Catalysis
Catalyst-Dependent Asymmetric Dearomative and Desymmetrizative Higher-Order [8 + 2] Cycloaddition of Indolizines with Maleimides toward the Atroposelective Synthesis of Cyclazines ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide The dearomatization of indolizines via higher-order [8 + 2] cycloadditions offers a direct route to the relevant core of cyclazines. However, surpassing the thermodynamic pathway that led to Friedel–Crafts-type conjugate addition adducts under catalytic conditions was never accomplished. Herein, we described that chiral phosphoric acids (CPAs) were able to favor the dearomative and desymmetrizative higher-order cycloaddition (HOC) between indolizines and maleimides, leading to atropoisomeric endo- cyclazines with high enantioselectivities (up to 98:2 e.r.). Theoretical calculations supported a kinetically favored stepwise cycloaddition pathway over the expected conjugated addition one. Notably, the latter was favored when the model phosphoric acid organocatalyst diphenyl phosphate was used instead of CPAs. Furthermore, a new mechanism for a key isomerization step, previously suggested as a sigmatropic event, in which the catalyst serves as a proton shuttle, was proposed.
2025 · Journal of the American Chemical Society
Pericyclic Umpolung in a Catalytic Asymmetric Diels–Alder Reaction of Tropone with Enol Ethers ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
One remarkable feature of catalysis in chemical synthesis is its capacity to override substrate-imposed reactivity and selectivity. The inversion of normal reaction patterns, commonly known as Umpolung, can be divided into (1) functional group Umpolung, where electrophilic groups are rendered nucleophilic (or vice versa), and (2) pericyclic Umpolung, in which the regioselectivity of pericyclic reactions is reversed relative to the predictions of frontier molecular orbital (FMO) theory. Although catalytic functional group Umpolung has been extensively investigated, the highly organized, concerted nature of pericyclic reactions makes inverting their conventional regioselectivity particularly challenging. To date, such inversion has been achieved only using engineered substrates or near-stoichiometric amounts of molecular cages. Here, we report an example of a chiral confined acid-catalyzed, asymmetric Umpolung of the Diels-Alder reaction. In our system, tropone reacts with enol ethers to deliver "contra-FMO" products with high yield, stereoselectivity, and regioselectivity. Mechanistic and computational studies indicate that a network of attractive noncovalent interactions, including π-π-interactions, nonclassical hydrogen bonding, and dispersion, governs the inverted regioselectivity. We anticipate that confined acid catalysis will open new avenues for addressing challenges in pericyclic Umpolung and regioselectivity control.
2025 · Nature Catalysis
Organocatalytic regio- and stereoselective cyclopropanation of olefins ↗Open accessFree PDF ↗Cyclopropane Reaction Mechanisms Abstract
Abstract As reactive intermediates and substructures of natural products and bioactive molecules, the smallest cyclic alkanes, cyclopropanes, are an attractive class of molecules for chemists. Arguably, the most general approach to their chemical synthesis involves the addition of metal carbenes to olefins. Whereas catalytic asymmetric cyclopropanations of electronically unbiased olefins with carbenoids have been reported using chiral metal complexes and engineered metalloenzymes, we now report a complementary, metal-free and highly enantioselective cyclopropanation of olefins with diazoalkanes, applying asymmetric counteranion-directed photoredox organocatalysis. We identify an ion pair featuring a thioxanthylium photoredox cation and a chiral imidodiphosphorimidate counteranion that catalyses highly enantioselective cyclopropanations of styrenes and aliphatic dienes with diazo compounds. Mechanistic investigations reveal a wavelength dependence of the enantioselectivity and suggest that the main catalytic pathway proceeds via olefin-derived radical cation intermediates. This metal-free, highly enantioselective organocatalytic approach complements previously reported methods for alkene manipulations.
2025 · Journal of the American Chemical Society
From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Even though chemists have long underappreciated the role of London dispersion in catalysis, its importance in determining a reaction course is now well recognized. Dispersion interactions have been shown to stabilize transition states and govern the stereoselectivity. In this context, the transfer hydrogenation of α,β-unsaturated aldehydes reported by our group via asymmetric counteranion-directed catalysis (ACDC) was revisited mechanistically. Previously, the use of an engineered Hantzsch ester featuring an isopropyl group was crucial for high enantioselectivity, suggesting London dispersion as an important stereocontrolling factor. Based on this hypothesis and the method's drawbacks (commercially unavailable Hantzsch ester, limited substrate scope, high catalyst loadings), we designed a broadly applicable second-generation catalyst system by introducing dispersion energy donors into the catalyst instead of the Hantzsch ester reagent. With the help of computational analysis, noncovalent interactions contributing to stereocontrol in the two systems were elucidated.
2025 · ACS Catalysis
Organocatalytic Asymmetric Synthesis of Azabicyclo[2.1.1]hexanes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide The bioisosteric replacement of 2D aromatic scaffolds with sp 3 -rich surrogates has become an important design element in modern medicinal chemistry. Within the sp 3 -rich world, the azabicyclo[2.1.1]hexane (aza-BCH) scaffold stands out as a pyrrolidine replacement and a useful building block. However, despite recent advancements in the field, a modular enantioselective synthesis of aza-BCHs remains challenging. In this study, we introduce an asymmetric organocatalytic approach relying on a confined imidodiphosphorimidate (IDPi) Brønsted acid that catalyzes the formal cycloaddition reaction of bicyclo[1.1.0]butanes (BCBs) with N -aryl imines under mild conditions, generating chiral aza-BCHs with high enantioselectivity (up to 99:1 er). Notably, the reaction proceeds effectively with a range of BCBs featuring ester, ketone, and amide functionalities. Experimental studies suggest that the reaction proceeds via a stepwise mechanism.
2025 · Nature Communications
Bis-indole chiral architectures for asymmetric catalysis ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Chiral scaffolds are essential to the advancement of asymmetric synthesis, yet the development of privileged motifs that more effectively communicate asymmetry constitutes a grand challenge for chemists. Here we describe a method using a confined chiral Brønsted acid catalyst to combine two inexpensive and widely available materials-indole and acetone-into a class of C₂-symmetric, spirocyclic compounds called SPINDOLE. SPINDOLEs extend the versatility of established frameworks by offering greater flexibility and ease of synthesis. The resulting chiral compounds can be readily modified to create diverse structures that excel in promoting highly selective reactions such as hydrogenation, allylic alkylation, hydroboration, and Michael addition. This work introduces a powerful strategy for advancing asymmetric catalysis, enabling the creation of versatile chiral frameworks with broad synthetic potential.
2025 · Journal of the American Chemical Society
Asymmetric Counteranion-Directed Halogen Bonding Catalysis ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
High Resolution Image Download MS PowerPoint Slide Halogen bonding has been established as a promising tool in organocatalysis. Asymmetric processes are nevertheless scarce, and their applications are limited to a few studies applying chiral halogen bond donors. Herein, we combine halogen bonding with asymmetric counteranion-directed catalysis, providing the first highly enantioselective example of such an approach. A strong bidentate iodine(III)-based catalyst with chiral disulfonimides as counteranions is applied in the first asymmetric organocatalysis of the Diels–Alder reaction between cyclopentadiene and trans -β-nitrostyrene, the key step in the synthesis of the drug fencamfamine, which was prepared with high enantioselectivity.
2025 · Journal of the American Chemical Society
Bronsted Acid-Catalyzed Reduction of Furans ↗Open accessFree PDF ↗Catalysis for Biomass Conversion Abstract
Bioderived furans play a pivotal role in advancing defossilized chemical pathways. The complete reduction of furans currently relies on impractical metal-catalyzed hydrogenations at high pressures and temperatures. In addition, the Birch reduction of unbiased furans to 2,5-dihydrofurans remains an unsolved synthetic challenge. Herein, we report a mild Bro̷nsted acid-catalyzed reduction of furans to 2,5-dihydro- and/or tetrahydrofuran derivatives using silanes as reducing agents. In particular, the first formal Birch reduction of furan itself is achieved. Mechanistic investigations reveal an intricate behavior of HFIP as the crucial solvent, preventing the intrinsic polymerization behavior of furans under acidic conditions and introducing additional driving force by specific product binding.
2024 · Journal of the American Chemical Society
Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated N-Boc-Formaldimine ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
High Resolution Image Download MS PowerPoint Slide Chiral 1,3-amino alcohols are ubiquitous structural motifs in natural products and active pharmaceutical ingredients. We present a highly enantioselective, inverse-electron-demand hetero-Diels–Alder reaction of olefins with in situ generated N -Boc-formaldimine catalyzed by strong and confined Bro̷nsted acids. This transformation provides direct access to valuable 1,3-amino alcohols from styrenes and 1,1-disubtituted alkenes. Isotope labeling studies and kinetic analysis reveal an unusual mechanism involving an oxazinium intermediate and a catalyst order greater than one.
2024 · Science
Catalytic asymmetric fragmentation of cyclopropanes ↗Cyclopropane Reaction Mechanisms
Abstract
The stereoselective activation of alkanes constitutes a long-standing and grand challenge for chemistry. Although metal-containing enzymes oxidize alkanes with remarkable ease and selectivity, chemical approaches have largely been limited to transition metal-based catalytic carbon-hydrogen functionalizations. Alkanes can be protonated to form pentacoordinated carbonium ions and fragmented into smaller hydrocarbons in the presence of strong Brønsted acids. However, catalytic stereocontrol over such reactions has not previously been accomplished. We show here that strong and confined acids catalyze highly enantioselective fragmentations of a variety of cyclopropanes into the corresponding alkenes, expanding the boundaries of catalytic selective alkane activation. Computational studies suggest the involvement of the long-debated cycloproponium ions.
2024 · Journal of the American Chemical Society
Highly Acidic Electron-Rich Brønsted Acids Accelerate Asymmetric Pictet–Spengler Reactions by Virtue of Stabilizing Cation–π Interactions ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide Electron-rich heteroaromatic imidodiphosphorimidates (IDPis) catalyze the asymmetric Pictet–Spengler reaction of N -carbamoyl-β-arylethylamines with high stereochemical precision. This particular class of catalysts furthermore provides a vital rate enhancement compared to related Brønsted acids. Here we present experimental studies on the underlying reaction kinetics that shed light on the specific origins of rate acceleration. Analysis of Hammett plots, kinetic isotope effects, reaction orders, Eyring plots, and isotopic scrambling experiments, allowed us to gather insights into the molecular interactions between the chiral Brønsted acid and catalytically formed intermediates. Based on rigorously determined p K a values as well as the experimental evidence, we propose that attractive intermolecular forces offered by electron-rich π-surfaces of the chiral counteranion enthalpically stabilize cationic intermediates and transition states by way of cation–π interactions. This view is furthermore supported by in-depth density functional theory calculations. Our deepened understanding of the reaction mechanism allowed us to develop a method for accessing 1-aryltetrahydroisoquinolines from aromatic dimethyl acetals, a substrate class that was thus far inaccessible via catalytic asymmetric Pictet–Spengler reactions.
2024 · Science
A solid noncovalent organic double-helix framework catalyzes asymmetric [6 + 4] cycloaddition ↗Organic Chemistry Cycloaddition Reactions
Abstract
Whereas [4 + 2] cycloadditions are among the most powerful tools in the chemist's synthetic arsenal, controlling reactivity and selectivity of [6 + 4] cycloadditions has proven to be extremely challenging. Such transformations, especially if compatible with simple hydrocarbon-based substrates, could ultimately provide a general approach to highly valuable and otherwise difficult to access 10-membered rings. We report here that highly acidic and confined imidodiphosphorimidate catalysts do not catalyze this reaction under homogeneous conditions. Notably, however, they can spontaneously precipitate an insoluble and double helix-shaped noncovalent organic framework, which acts as a distinctively reactive and stereoselective catalyst of [6 + 4] cycloadditions of simple dienes with tropone.
2024 · Nature
The catalytic asymmetric polyene cyclization of homofarnesol to ambrox ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
Abstract Polyene cyclizations are among the most complex and challenging transformations in biology. In a single reaction step, multiple carbon–carbon bonds, ring systems and stereogenic centres are constituted from simple, acyclic precursors1–3. Simultaneously achieving this kind of precise control over product distribution and stereochemistry poses a formidable task for chemists. In particular, the polyene cyclization of (3E,7E)-homofarnesol to the valuable naturally occurring ambergris odorant (−)-ambrox is recognized as a longstanding challenge in chemical synthesis1,4–7. Here we report a diastereoselective and enantioselective synthesis of (−)-ambrox and the sesquiterpene lactone natural product (+)-sclareolide by a catalytic asymmetric polyene cyclization by using a highly Brønsted-acidic and confined imidodiphosphorimidate catalyst in the presence of fluorinated alcohols. Several experiments, including deuterium-labelling studies, suggest that the reaction predominantly proceeds through a concerted pathway in line with the Stork–Eschenmoser hypothesis8–10. Mechanistic studies show the importance of the enzyme-like microenvironment of the imidodiphosphorimidate catalyst for attaining exceptionally high selectivities, previously thought to be achievable only in enzyme-catalysed polyene cyclizations.
2024 · Synfacts · editorial
C 2-Symmetric Chiral Thiol-Catalyzed Hydrogen Atom Transfer for Asymmetric Hydroamination ↗Radical Photochemical Reactions
Abstract
Key words thiol catalysis - photocatalysis - radical cations - hydrogen atom transfer - hydroamination Publication History Article published online: 25 July 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Engaging Furans in Photocycloaddition to Access Molecular Cages ↗Organic Chemistry Synthesis Methods
Abstract
Key words furans - chromones - cycloaddition Publication History Article published online: 25 July 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Lysine as a ‘Smart’ Amine Donor for Transaminase-Catalyzed Synthesis of β-Branched Amino Acids ↗Enzyme Catalysis and Immobilization
Abstract
Key words transaminase - non-canonical β-branched amino acids - lysine Publication History Article published online: 25 July 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Nature Communications
Organocatalytic asymmetric synthesis of Si-stereogenic silacycles ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
A strong and confined Brønsted acid catalyzed enantioselective cyclization of bis(methallyl)silanes provides enantioenriched Si-stereogenic silacycles. High enantioselectivities of up to 96.5:3.5 er were obtained for a range of bis(methallyl)silanes. NMR and ESI-MS studies reveal that the formation of a covalent adduct irreversibly inhibits turnover. Remarkably, we found that acetic acid as an additive promotes the collapse of this adduct, enabling full turnover. Experimental investigation and density functional theory (DFT) calculations were conducted to elucidate the origin of this phenomenon and the observed enantioselectivity.
2024 · Synfacts · editorial
Organocatalytic Stereodivergent Intramolecular Synthesis of Spiroaminals ↗Asymmetric Synthesis and Catalysis
Abstract
Key words stereodivergent synthesis - spiroaminals - intramolecular cyclization - hydrogen-bonding organocatalysis - DyKAT Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
N-Heterocyclic Carbenes Catalyze the Formation of Fused 6-5-5 Tricyclic Natural-Product Frameworks ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Key words N-heterocyclic carbenes - annulation - tricycloundecanes - ynals Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Brønsted Acid Catalyzes Intramolecular Allylic Substitution Reaction of Allylic Alcohols ↗Asymmetric Synthesis and Catalysis
Abstract
Key words allylic alcohol - Brønsted acids - intramolecular reaction - allylic substitution - 2-vinylchromans - metal-free reactions Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Hydrodeamination through in situ Generation of Diazonium Species by ortho-Naphthoquinone Catalysis ↗Oxidative Organic Chemistry Reactions
Abstract
Key words hydrodeamination - ortho -quinones - diazonium - aryl amines Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Photocatalysis Enables the Hydroamidation of Alkenes Using Sulfonyl Azides and Hantzsch Esters ↗Free to readFree PDF ↗Radical Photochemical Reactions Abstract
Key words photocatalysis - hydroamidation - sulfonyl azides - alkenes - anti-Markovnikov Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Decarboxylative Sulfhydrylation of Carboxylic Acids Enabled by Multimodal Acridine Photocatalysis ↗Radical Photochemical Reactions
Abstract
Key words multimodal photocatalysis - acridine - PCET-catalysis Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Organocatalytic Asymmetric Construction of Vicinal Stereocenters via α-Alkylation ↗Asymmetric Synthesis and Catalysis
Abstract
Key words enamine catalysis - alkylation - aldehydes - vicinal stereocenters - quaternary stereocenters Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Stereodivergent Radical Cyclizations Enabled by Directed Evolution of Fatty Acid Photodecarboxylases ↗Enzyme Catalysis and Immobilization
Abstract
Key words biocatalysis - directed evolution - asymmetric catalysis - stereodivergence Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Asymmetric Photoredox Catalytic de Mayo Reaction ↗Radical Photochemical Reactions
Abstract
Key words de Mayo reaction - photoredox catalysis - sensitization - dicyanopyrazine - pyrenyl Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Photocatalyst Enables the Phosphonylation of Unactivated C(sp3)–H Bonds ↗Radical Photochemical Reactions
Abstract
Key words radicals - organocatalysis - phosphonylation - C–H activation - 1,5-HAT - energy transfer Publication History Article published online: 14 June 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Cooperative Photoredox and Chiral Brønsted Acid Catalysis Permits Asymmetric [2π+2σ] Cycloaddition ↗Free to readFree PDF ↗Radical Photochemical Reactions Abstract
Key words asymmetric photoredox catalysis - Brønsted acid catalysis - [2π+2σ] cycloaddition - bicyclobutanes Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Cinchona Phosphinate-Catalyzed Desymmetrization of Sulfonimidamides ↗Asymmetric Synthesis and Catalysis
Abstract
Key words asymmetric catalysis - cinchona alkaloids - sulfonimidamides - sulfur(VI) compounds - acylation - desymmetrization - high-throughput experimentation Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Photoenzymatic Hydroalkylation of Olefins toward Chiral α‑Chloroamides ↗Enzyme Catalysis and Immobilization
Abstract
Key words ‘ene’-reductase - flavin hydroquinone - α‑chloroamides - photoenzyme - hydroalkylation - olefins Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Efficient Asymmetric Syntheses of Chiral Imines with Multi-Stereocenters ↗Asymmetric Synthesis and Catalysis
Abstract
Key words kinetic resolution - organocatalysis - umpolung - enantioselectivity - trifunctional - chiral ammonium catalysts - protonation Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Potassium-ACDC of the Wittig Reaction ↗Phosphorus compounds and reactions
Abstract
Key words Wittig olefination - axial chirality Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Light-Governed Chemoselectivity in Organocatalytic C(sp2)–X Couplings ↗Radical Photochemical Reactions
Abstract
Key words iodobromoarenes - coupling - chromoselectivity - helicenium Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Pivalate Salt-Catalyzed, Bis(silyl)acetamide-Mediated Silylation of Terminal Alkynes ↗Organoboron and organosilicon chemistry
Abstract
Key words alkynes - pivalate - silylation - base catalysis Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Silylium Ions Catalyze the Regioselective and Diastereoselective Thiosilylation of C–C Multiple Bonds ↗Sulfur-Based Synthesis Techniques
Abstract
Key words difunctionalization of C–C multible bonds - thiosilylation - alkynes - allenes - silylium ions - sulfonium ions Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Harnessing N-Heterocyclic Carbene Catalytic Activity into Stereoselective Synthesis of Chiral Cyclophanes ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Key words planar-chiral cyclophanes - N-heterocyclic carbenes - macrocycles - dynamic kinetic resolution Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Organophotocatalytic Construction of Sulfonamides from Dibenzothiophenium Salts ↗Radical Photochemical Reactions
Abstract
Key words sulfonamides - photoredox catalysis - multicomponent coupling Publication History Article published online: 14 May 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Regiodivergent Radical Termination for Intermolecular Biocatalytic C–C Bond Formation ↗Free to readFree PDF ↗Enzyme Catalysis and Immobilization Abstract
Key words reductases - biocatalysis - regioselectivity - unsaturated ketones - C–C coupling - hydroalkylation
2024 · Synfacts · editorial
Organocatalytic Photoinduced Diastereoselective 1,2-Sulfonylsulfination of Alkenes ↗Radical Photochemical Reactions
Abstract
Key words photoredox catalysis - alkene disulfurization - multicomponent coupling Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Flavin-Photocatalytic Sulfide α-C–H Functionalization Using Arylsulfonyl Multiple-Bond Reagents ↗Radical Photochemical Reactions
Abstract
Key words flavin - photocatalysis - sulfides - C–H functionalization Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Enantioselective Control Over α-Iminonitriles with a Novel Bifunctional Superbase-Thiourea Organocatalyst ↗Asymmetric Synthesis and Catalysis
Abstract
Key words pyrrolines - thiourea - superbase Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Stereoselective Synthesis of α-Aminonitriles, Catalyzed by Hydrogen-Bonding Donors ↗Asymmetric Synthesis and Catalysis
Abstract
Key words unnatural amino acids - hydrogen-bonding donors - aminonitriles Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Mesoionic N-Heterocyclic Olefin Catalyzes Formylation of Thiols via CO2 Trapping ↗Carbon dioxide utilization in catalysis
Abstract
Key words mesoionic compounds - thiols - formylation - carbon dioxide - isotopic labeling Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Organocatalytic Nucleophilic Desymmetrization of P(V) Precursors ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Key words phosphorus - organocatalysis - desymmetrization - enantioselectivity - bifunctional iminophosphorane - pinacol borane Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Diazaphospholene Hydrides Catalyze Enantioselective Reductive Eschenmoser–Claisen Rearrangements ↗Asymmetric Synthesis and Catalysis
Abstract
Key words asymmetric catalysis - pericyclic reaction - [3,3]-sigmatropic rearrangement - Eschenmoser–Claisen rearrangement - 1,3,2-diazaphospholene hydrides Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Enzymatic Cleavage of Silicon–Carbon Bonds in Siloxanes ↗Enzyme Catalysis and Immobilization
Abstract
Key words volatile methylsiloxanes - Si–C bond cleavage - directed evolution - biodegradation - cytochrome P450 BM3 Publication History Article published online: 15 April 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Catalytic Enantioselective Wagner–Meerwein Rearrangement of Alkenyl Cycloalkanes ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Key words IDPi catalysis - aliphatic hydrocarbons - Wagner–Meerwein rearrangement Publication History Article published online: 13 March 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
VANOL-Derived Imidodiphosphorimidate-Catalyzed Bromospiroketalization ↗Asymmetric Synthesis and Catalysis
Abstract
Key words imidopdiphosphorimidate - bromo spiroketalization - asymmetric organocatalysis - VANOL Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Enzymatic C–H Amidation toward Stereoselective Construction of β-, γ- and δ-Lactams ↗Free to readFree PDF ↗Synthesis and Catalytic Reactions Abstract
Key words C–H amidation - myoglobin - dioxazolones - enantiodivergence - nitrene transfer Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Metal-free meta-Selective C–H Amination of Arenes ↗Synthesis and Catalytic Reactions
Abstract
Key words late-stage derivatization - amination - arenes Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Acid-Catalyzed Nitromethane Activation for the Synthesis of Amides and Nitriles ↗Chemical Synthesis and Reactions
Abstract
Key words acid catalysis - ketones - aldehydes - alkynes - amides - nitriles Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Stereoselective α-Benzylation of Cyclic Ketones via Chemoenzymatic Cascade ↗Enzyme Catalysis and Immobilization
Abstract
Key words chemoenzymatic cascade - aldol condensation - ene-reductase - α-benzylation Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Enantioselective C−C Bond Insertion into Aldehydes via Oxazaborolidinium Catalyzed 1,2-Acyl Shift ↗Asymmetric Synthesis and Catalysis
Abstract
Key words COBI-catalyst - C–C bond insertion - all-carbon quaternary stereocenters Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Biocatalytic Approach for the Synthesis of Lactones via Carbene C–H Insertion ↗Cyclopropane Reaction Mechanisms
Abstract
Key words carbene transferase - P411 - diazo compounds - lactones - C–H functionalization Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Brønsted Acid Catalyzed Aromatization-Enabled Umpolung of Imines ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Key words umpolung - organocatalysis - enantioselectivity - chiral phosphoric acid - atropisomers - aromatization - imines Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Asymmetric Cyclizations Catalyzed by Chiral Boryl Radicals ↗Asymmetric Synthesis and Catalysis
Abstract
Key words asymmetric catalysis - N-heterocyclic carbenes - boranes - alkynes Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · Synfacts · editorial
Photoenzymatic Hydrosulfonylation of Olefins Initiated by Single Electron Oxidation ↗Radical Photochemical Reactions
Abstract
Key words asymmetric catalysis - organocatalysis - hydrosulfonylation - ene-reductase - photoenzymes - oxidation-initiated reaction - donor–acceptor complexes Publication History Article published online: 14 February 2024 © 2024. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2024 · The Cambridge Structural Database · dataset
CCDC 2248971: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2024 · The Cambridge Structural Database · dataset
CCDC 2248970: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2024 · The Cambridge Structural Database · dataset
CCDC 2248972: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2024 · Nature
Catalytic asymmetric cationic shifts of aliphatic hydrocarbons ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract Asymmetric catalysis is an advanced area of chemical synthesis, but the handling of abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in the substrates and reagents to facilitate an efficient interaction with the chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically to enable the processing of small unbiased substrates1. However, asymmetric reactions in which both substrate and product are purely aliphatic hydrocarbons have not previously been catalysed by such super strong and confined acids. We describe here an imidodiphosphorimidate-catalysed asymmetric Wagner–Meerwein shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. Despite their long history and high relevance for chemical synthesis and biosynthesis, Wagner–Meerwein reactions utilizing purely aliphatic hydrocarbons, such as those originally reported by Wagner and Meerwein, had previously eluded asymmetric catalysis.
2024 · ACS Catalysis
Acid-Catalyzed Oxy-aminomethylation of Styrenes ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
High Resolution Image Download MS PowerPoint Slide We report a strong Brønsted acid-catalyzed three-component oxy-aminomethylation of styrenes with sym -trioxane and sulfonamides or carbamates. This transformation provides a variety of 1,3-oxazinanes in moderate to good yields under mild reaction conditions. The obtained heterocycles can be readily transformed into the corresponding 1,3-amino alcohols, which are useful building blocks for the synthesis of pharmaceutically relevant molecules. Mechanistic studies suggest the intermediacy of an in situ formed 1,3,5-dioxazinane and a subsequent reaction with the olefin.
2023 · Synfacts · editorial
Tandem N-Heterocyclic Carbene/Photocatalysis Approach for the Synthesis of Amino Esters ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Key words photocatalysis - N-heterocyclic carbene - amino esters - imidyl radicals Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Parallel Kinetic Resolution of Aziridines with Nucleophilic Water Aided by Acyloxy Borrowing ↗Synthesis and Catalytic Reactions
Abstract
Key words parallel kinetic resolution - β-amino alcohols - aziridines - chiral phosphoric acids Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Enantioselective C–C, C–O and C–N Bond Formation with Intermediacy of a Benzylic Secondary Cation ↗Asymmetric Synthesis and Catalysis
Abstract
Key words benzylic carbocation - ACDC - asymmetric S N 1 reaction Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photocatalytic syn-Selective Thioalkynylation, Thiovinylation and Thioallylation of Bicyclobutanes ↗Radical Photochemical Reactions
Abstract
Key words photocatalysis - bicyclobutanes - thioalkynylation - thiovinylation - thioallylation Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Ene-Reductase: Catalyst for the Photoenzymatic Stereoselective Synthesis of Benzo-Fused Heterocycles ↗Radical Photochemical Reactions
Abstract
Key words benzo-fused heterocycles - ene-reductase - photoenzymatic synthesis - benzoxepinones Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Enynes Difluorination via Iodine(I/III) Catalysis ↗Fluorine in Organic Chemistry
Abstract
Key words enynes - 1,1-difluorination - iodine(I/III) - 1,2-alkynyl shift Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Rendering Catalyst Alkylation Reversible Enables Conjugate Addition toward Fluoroalkyl γ-Nitroolefins ↗Asymmetric Synthesis and Catalysis
Abstract
Key words conjugate addition - fluoroalkyl aldehydes - nitroolefins - peptide catalysis - catalyst alkylation Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
One-Pot Asymmetric Synthesis of Oxa[5]helicene Scaffolds ↗Synthesis and Properties of Aromatic Compounds
Abstract
Key words cascade process - helicene scaffolds - one-pot synthesis - dynamic kinetic resolution - Michael addition Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Stable Vinyl Sulfoxonium Ylides with Chiral Acyl Atropisomers ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Key words asymmetric catalysis - atropisomerism - sulfoxonium ylides - rotational barrier - Brønsted acids Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Arenium Carborates Catalyze the Halodealkylation of Tetraalkyl Silanes ↗Free to readFree PDF ↗Organoboron and organosilicon chemistry Abstract
Key words silanes - carborates - halodealkylation Publication History Article published online: 08 December 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Journal of Synthetic Organic Chemistry Japan
Enthusiasm, Guiding the Way to Universal Catalysts? ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis 2023 · Science
Taming secondary benzylic cations in catalytic asymmetric S N 1 reactions ↗Asymmetric Synthesis and Catalysis
Abstract
Benzylic stereogenic centers are ubiquitous in natural products and pharmaceuticals. A potentially general, though challenging, approach toward their selective creation would be asymmetric unimolecular nucleophilic substitution (S N 1) reactions that proceed through highly reactive benzylic cations. We now report a broadly applicable solution to this problem by identifying chiral counteranions that pair with secondary benzylic cations to engage in catalytic asymmetric C−C, C−O, and C−N bond-forming reactions with excellent enantioselectivity. The critical cationic intermediate can be accessed from different precursors via Lewis- or Brønsted acid catalysis. Key to our strategy is the use of only weakly basic, confined counteranions that are posited to prolong the lifetime of the carbocation, thereby avoiding nonproductive deprotonation pathways to the corresponding styrene.
2023 · Synfacts · editorial
Spiro Phosphoric Acid-Catalyzed Amination Reaction of In Situ-Generated Ketenes Toward α-Chiral Amides ↗Asymmetric Synthesis and Catalysis
Abstract
Key words Wolff rearrangement - chiral amides - phosphoric acid catalysis - visible-light photoactivation Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Organocatalytic Friedel–Crafts Reaction of Unactivated Arenes ↗Organic and Inorganic Chemical Reactions
Abstract
Key words Friedel–Crafts reaction - arylglycines - IDPi - arenes - alkylbenzenes Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Asymmetric [2+2] Photocycloaddition to Truxinates by Brønsted Acid-Catalyzed Chromophore Activation ↗Radical Photochemical Reactions
Abstract
Key words photocycloaddition - acid catalysis - chromophore activation - truxinates - natural products Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Stereoselective Synthesis of Cyclopropane Derivatives from Mixtures of (E)- and (Z)-Enol Acetates ↗Cyclopropane Reaction Mechanisms
Abstract
Key words [2+1] cyclopropanation - carbene transferase - enol acetates - polysubstituted cyclopropanes Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Lewis Acid-Catalyzed C–F Bond Activation and Functionalization ↗Fluorine in Organic Chemistry
Abstract
Key words Lewis acid catalysis - cyclopropanes - cyclopropenium ion - C–F bond cleavage - silyl ketene acetals - nucleophilic addition - difluorocyclopropenes Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Stereoselective Synthesis of Noncanonical Amino Acids Enabled by Photoredox-Pyridoxal Radical Biocatalysis ↗Radical Photochemical Reactions
Abstract
Key words asymmetric catalysis - photoredox catalysis - pyridoxal radical biocatalysis - amino acids Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Isoquinoline-Forming Staudinger–aza-Wittig Reaction Enabled by Atroposelective PIII/PIV=O Redox Catalysis ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Key words Staudinger–aza-Wittig - QUINOX - QUINAP - atroposelectivity Publication History Article published online: 14 October 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · CHEMKON
Mit Begeisterung für Wissenschaft für die Zukunft gewappnet ↗Free to readFree PDF ↗Chemistry Education and Research Abstract
Ich bin Optimist und liebe das Leben auf diesem wunderschönen Planeten. Aber es lässt sich nicht leugnen: Die fossilen Ressourcen dieser Erde neigen sich dem Ende. Das Klima wird menschenunfreundlicher. Sauberes Trinkwasser und genügend Nahrung werden bei einer noch weiterwachsenden Weltbevölkerung zu einem immer größeren Problem. Pandemien stellen Mediziner und Pharmazeuten vor immer neue Herausforderungen. Und irgendwann, seien wir ehrlich, überlassen wir diesen ganzen Haufen an Schwierigkeiten unseren Kindern, unseren Enkeln. Den Menschen, die jetzt – oder in den kommenden Jahren – als Schülerinnen und Schülern in Ihren Klassenräumen sitzen. Ist die nächste Generation in der Lage, all das zu meistern? Wie kann es uns gelingen, ihnen das nötige Rüstzeug dafür zu geben? Die Antwort ist so banal wie offensichtlich: Wir müssen sie ausbilden. Und das beinhaltet neben dem reinen Vermitteln von Wissen vor allem eines – wir müssen sie für die Wissenschaft begeistern. Ich war noch sehr jung, als für mich feststand, dass ich Chemiker werden wollte. Chemiker verstehen die Welt, dachte ich. Immerhin können sie alle Dinge bis auf atomare Ebene untersuchen. In meiner Begeisterung richtete ich als Elfjähriger gemeinsam mit einem Freund in einem Frankfurter Keller mein erstes Labor ein. Vom Apotheker, der im Erdgeschoss sein Ladenlokal hatte, besorgten wir uns alle möglichen Utensilien. Wir hatten dem Mann erzählt, wir wollten Waschmittel für unsere Mütter herstellen. In Wahrheit hatten wir es auf Schwarzpulver abgesehen. Es war alles wahnsinnig spannend und machte uns großen Spaß. Erst, als ein Versuch schiefging und dicke Rauchschwaden aus dem Kellerfenster quollen, merkte der Apotheker, dass wir wohl doch kein Waschmittel herstellen wollten. Über die berechtigte Frage, ob er nicht gleich bei der Zutatenliste hätte Verdacht schöpfen müssen, legen wir einmal den Mantel des Schweigens. Auch wenn der Apotheker uns nach dem Vorfall den Nachschub an Chemikalien verwehrte, und auch wenn ich heute weiß, dass Chemiker natürlich nicht immer alles verstehen, so ist meine Leidenschaft für die Chemie geblieben. Denn sie ist eine wunderschöne, kreative Wissenschaft und zudem von unglaublicher Bedeutung für die Zukunft der Menschheit. Ob es um alternative Energiequellen geht, um die Etablierung einer Kreislaufwirtschaft, um neue wirksame Medikamente: Ohne Chemikerinnen und Chemiker werden wir die Probleme der Menschheit nicht lösen können. Heute würde ich natürlich niemandem empfe
2023 · Synfacts · editorial
Direct, Additive-Free Electrochemical Dehydrative Esterification of Carboxylic Acids and Alcohols ↗Chemical Synthesis and Reactions
Abstract
Key words esterification - phenothiazine - electrocatalysis - dehydration - alcohols - carboxylic acids Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photosensitized O2Permits a Versatile Cyclopropanation Reaction ↗Cyclopropane Reaction Mechanisms
Abstract
Key words cyclopropanation - organocatalysis - photoredox catalysis - unactivated alkenes - oxygen - radical reaction Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Synthesis of Eight-Membered Carbocycles by (I)/I(III)-Catalyzed Diene Cyclization ↗Free to readFree PDF ↗Oxidative Organic Chemistry Reactions Abstract
Key words hypervalent iodine - 1,3-dienes - cyclooctenes - fluorination - carbofunctionalization Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
N-Triflyl Phosphoramide Catalyzed Atroposelective C–C Cross-Coupling of 1-Azonaphthalenes ↗Axial and Atropisomeric Chirality Synthesis
Abstract
Key words atroposelectivity - N -triflyl phosphoramide - cross-coupling - organocatalysis - axially chirality - remote control Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Ene-Reductase Outcompetes Hydrogen Atom Transfer in Asymmetric Carbohydroxylation of Alkenes ↗Enzyme Catalysis and Immobilization
Abstract
Key words ‘ene’-reductase - photoenzymatic catalysis - flavin cofactor Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Cytochrome P450-Derived Ketone Synthase Enables Regioselective Aerobic Oxidation of Arylalkenes ↗Metal-Catalyzed Oxygenation Mechanisms
Abstract
Key words cytochrome P450 - protein engineering - arylalkenes - benzylketones Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photoredox Catalysis Enables New Synthetic Route Toward Oxetanes ↗Radical Photochemical Reactions
Abstract
Key words oxetanes - alcohols - C–H functionalization - photoredox catalysis - hydrogen atom transfer Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Enantioselective Protio-Semipinacol Rearrangement of Vinyl Cyclopropanols ↗Cyclopropane Reaction Mechanisms
Abstract
Key words asymmetric catalysis - protio-semipinacol rearrangement - vinyl cyclopropanols - cyclobutanones Publication History Article published online: 14 September 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Biocatalysis and Photocatalysis Joining Forces in a Stereoselective Method for Synthesis of Sulfones ↗Enzyme Catalysis and Immobilization
Abstract
Key words chiral sulfones - old yellow enzyme - photoenzymatic reaction - hydrosulfonylation Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Engineered Photoenzyme Overrides Traditional Regioselectivities in the Alkylation of Indoles ↗Enzyme Catalysis and Immobilization
Abstract
Key words ene reductase - photoenzymes - S E Ar reaction - regioselective alkylation - indoles - protein engineering Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Enantioselective Nucleophilic Desymmetrization of Phosphonate Esters Using Bifunctional Superbases ↗Organophosphorus compounds synthesis
Abstract
Key words asymmetric catalysis - suberbases - iminophosphoranes - desymmetrization - phosphonate esters - phosphorus(V) compounds - phenols Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photocatalytic Z to E Isomerisation of Fluorinated β-Borylacrylates ↗Radical Photochemical Reactions
Abstract
Key words alkenyl fluorides - amide bond isosteres - energy transfer - photocatalysis Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Chiral-Phosphoric-Acid-Catalyzed Asymmetric Dearomatization of Indole Derivatives ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Key words asymmetric dearomatization - indoles - rearrangement - azodicarboxylates Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Imidodiphosphorimidates(IDPis) Permit Asymmetric Synthesis of cis-Tetrahydrocannabinoids ↗Asymmetric Synthesis and Catalysis
Abstract
Key words tetrahydrocannabinoids - organocatalysis - confined - imidodiphosphorimidates - allylic cation - biomimetic synthesis Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Bifunctional Iminophosphorane Catalyst Enables Challenging Intramolecular Oxa-Michael Reactions ↗Phosphorus compounds and reactions
Abstract
Key words oxa-Michael reaction - base catalysis - intramolecular reaction - bifunctional iminophosphorane - tetrahydrofurans - tetrahydropyrans Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
CO2 Reduction by a Membranous, Metal-Free, Triazine- and Imine-Containing Covalent Organic Framework ↗Covalent Organic Framework Applications
Abstract
Key words covalent organic frameworks - granular materials - membranes - CO 2 reduction - photocatalysis Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
An Effcient Organocatalytic Chlor-Alkali Process ↗Carbon dioxide utilization in catalysis
Abstract
Key words chlorine - amides - electrolysis - carbon dioxide Publication History Article published online: 14 July 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · The Cambridge Structural Database · dataset
CCDC 2263055: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2023 · The Cambridge Structural Database · dataset
CCDC 2263056: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2023 · Journal of the American Chemical Society
Asymmetric Catalytic Friedel–Crafts Reactions of Unactivated Arenes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide Since its discovery more than a century ago, the Friedel–Crafts reaction has manifested itself as a powerful method for the introduction of carbon substituents to arenes. Despite its potential generality, the scope of the reaction is intrinsically limited by the arene’s nucleophilicity, which has previously restrained the applicability of asymmetric variants to activated substrates. To overcome this fundamental limitation, we report herein an asymmetric Friedel–Crafts reaction of unactivated, purely hydrocarbon arenes, alkoxybenzenes, and heteroarenes with N, O -acetals to give enantioenriched arylglycine esters. Highly regio- and stereoselective C–C bond formation was achieved using strong and confined Brønsted acid organocatalysts, enabling the first asymmetric catalytic Friedel–Crafts reaction of simple alkylbenzenes.
2023 · Angewandte Chemie International Edition
Direct Regioselective Dehydrogenation of α‐Substituted Cyclic Ketones ↗Open accessFree PDF ↗Oxidative Organic Chemistry Reactions Abstract
We disclose a highly regioselective, catalytic one-step dehydrogenation of α-substituted cyclic ketones in the presence of 2,3-dichlorobenzo-5,6-dicyano-1,4-benzoquinone (DDQ). The high regioselectivity originates from a phosphoric acid-catalyzed enolization, selectively affording the thermodynamically preferred enol, followed by the subsequent oxidation event. Our method provides reliable access to several α-aryl and α-alkyl substituted α,β-unsaturated ketones.
2023 · Angewandte Chemie
Direkte Regioselektive Dehydrierung von α‐Substituierten Cyclischen Ketonen ↗Open accessFree PDF ↗Oxidative Organic Chemistry Reactions Abstract
Abstract Wir berichten über eine hochregioselektive, katalytische einstufige Dehydrierung von α‐substituierten cyclischen Ketonen in Gegenwart von 2,3‐Dichlorbenzo‐5,6‐dicyano‐1,4‐benzochinon (DDQ). Die exzellente Regioselektivität beruht auf einer Phosphorsäure‐katalysierten Enolisierung, die selektiv das thermodynamisch bevorzugte Enol liefert. Die anschließende Oxidation ermöglicht einen zuverlässigen Zugang zu mehreren α‐Aryl‐ und α‐Alkyl‐substituierten α,β‐ungesättigten Ketonen.
2023 · Angewandte Chemie
Auf dem Weg zu einer Formyl‐zu‐Phenyl‐Reaktion: Eine unerwartete photochemische Fulven‐Umlagerung ↗Open accessRadical Photochemical Reactions
Abstract
Abstract Um Aldehyde in Arene zu überführen, haben wir eine Sequenz entworfen, bei der ein Aldehyd zunächst zu einem Fulven umgesetzt wird. Daraufhin folgen photochemische und platinkatalysierte Umlagerungen zu einem Dewar‐Benzol‐Derivat, welches schließlich in das gewünschte Aren isomerisiert. Obwohl theoretische Berechnungen die Plausibilität dieses Weges nahelegen, stellten wir experimentell fest, dass die Fulven‐Bestrahlung zu einer unerwarteten Isomerisierung in ein Spiro[2.4]heptadien führt. Diese ungewöhnliche Photoumlagerung wurde mechanistisch untersucht und ermöglicht den Zugang zu verschiedenen Spiro[2.4]heptadienen mit unterschiedlichen Substituenten.
2023 · Angewandte Chemie International Edition
Toward a Formyl‐to‐Phenyl Conversion: An Unexpected Photochemical Fulvene Rearrangement ↗Open accessFree PDF ↗Photolysis and Reactive Intermediates Abstract
Toward a conversion of aldehydes into arenes, we designed a sequence involving the initial reaction of an aldehyde to give a fulvene, followed by photochemical and platinum-catalyzed rearrangements into a Dewar benzene derivative, which finally isomerizes into the targeted arene. While computational studies support the plausibility of this route, we found that fulvene irradiation resulted in an unexpected isomerization into a spiro[2.4]heptadiene. This unusual photorearrangement has been investigated mechanistically and provides access to a variety of spiro[2.4]heptadienes with different substituents.
2023 · Synfacts · editorial
BINOL Catalysis Permits One-Pot Synthesis of Chiral Trifluoromethyl and Trimethylsilyl Allenols ↗Asymmetric Synthesis and Catalysis
Abstract
Key words trifluoromethyl allenols - asymmetric organocatalysis - BINOL - diazomethanes - alkynyl boronates Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Towards Efficient Synthesis of Chiral β-Amino Amides via Organocatalysis ↗Multicomponent Synthesis of Heterocycles
Abstract
Key words multicomponent - organocatalysis - amino amides - Brønsted acid - Ugi reaction - ynamides Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Enantioselective Iminium Catalysis-Mediated Vinylcyclopropane–Cyclopentene Rearrangement ↗Cyclopropane Reaction Mechanisms
Abstract
Key words vinylcyclopropane rearrangement - iminium catalysis - cyclopentenes - DYKAT Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Regioselective meta-Amination of Arylamines Enabled by in situ Generated Quinone Imine Ketals ↗Catalytic C–H Functionalization Methods
Abstract
Key words meta -substituted anilines - anti-psychotic drugs - quinone imine ketals Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Methionine Sulfoxide Reductase as an Efficient Catalyst for Kinetic Resolution of the Chiral Sulfoxides ↗Enzyme Catalysis and Immobilization
Abstract
Key words chiral sulfoxides - kinetic resolution - reductases - rational mutagenesis Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Asymmetric Conjugate Hydrocyanation of Enals via SET-Induced Umpolung ↗Radical Photochemical Reactions
Abstract
Key words asymmetric catalysis - aminocatalysis - photoredox catalysis - conjugate addition - hydrocyanation - enals Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Engineered Methyltransferase-Catalyzed Terminal Prenyl Group Tail Methylation of Linear Terpenoids ↗Free to readFree PDF ↗Enzyme Catalysis and Immobilization Abstract
Key words methylation - alkenes - terpenoids - methyltransferases Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Organocatalytic Enantioselective Reductive Radical Coupling of Ketimines with Dihydropyridines ↗Radical Photochemical Reactions
Abstract
Key words photoredox catalysis - chiral Brønsted acid catalysis - α-amino acids Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Novel C2-Symmetric Borinic Acids Expand the Scope of Boron-Based Catalysts for Asymmetric Transformations ↗Asymmetric Synthesis and Catalysis
Abstract
Key words borinic acids - asymmetric catalysis - desymmetrization - propanediols Publication History Article published online: 16 June 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synlett
Brønsted Acid Catalyzed Asymmetric Silylation of Biaryl Diols ↗Open accessFree PDF ↗Axial and Atropisomeric Chirality Synthesis Abstract
Abstract We report a Brønsted acid catalyzed enantioselective silylation of biaryl diols with an allylsilane as a silicon source. This process enables facile access to enantioenriched biaryl silyl ethers with an axial stereogenicity. A control experiment supports a mechanism proceeding by desymmetrization followed by kinetic resolution.
2023 · Asian Journal of Organic Chemistry
Synthesis and Resolution of an Axially Chiral Spirocyclic Quaternary Ammonium Ion‐Based Phase‐Transfer Catalyst ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract We report the synthesis of a novel spirocyclic quaternary ammonium salt that possesses axial chirality. Enantiopure material was obtained by fractional crystallization of the corresponding (R,R)‐tartrate salt. Application of this chiral quaternary ammonium salt in phase‐transfer catalytic asymmetric alkylation of glycinate Schiff base was examined.
2023 · Journal of the American Chemical Society
A Catalytic Asymmetric Hydrolactonization ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Despite recent advancements in the development of catalytic asymmetric electrophile induced lactonization reactions of olefinic carboxylic acids, the archetypical hydrolactonization has long remained an unsolved and well-recognized challenge. Here, we report the realization of a catalytic asymmetric hydrolactonization using a confined imidodiphosphorimidate (IDPi) Brønsted acid catalyst. The method is operationally simple, scalable, and compatible with a wide variety of substrates. Its potential is showcased with concise syntheses of the sesquiterpenes (-)-boivinianin A and (+)-gossonorol. Through in-depth physicochemical and DFT analyses, we derive a nuanced picture of the mechanism and enantioselectivity of this reaction.
2023 · Synfacts · editorial
Hydrogen-Bond-Donor Catalyst Permits Asymmetric Transformation of Sulfonyl Cyanides toward Sulfinates ↗Asymmetric Synthesis and Catalysis
Abstract
Key words hydrogen-bond-donor catalysis - sulfinyl compounds - asymmetric deoxygenation Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Carbene Transferases as Catalysts for Chemodivergent Activation of C(sp2)–H and C(sp3)–H Bonds ↗Cyclopropane Reaction Mechanisms
Abstract
Key words cyanomethylation - C–H bond activation - carbene transferase - enzyme engineering - cytochromes Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Identification of a Pericyclase that Catalyzes the Formation of cis-Decalins ↗Organic Chemistry Cycloaddition Reactions
Abstract
Key words pericyclase - intramolecular Diels–Alder reaction - cis -decalin - shape complementarity Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Conformation-Switching DNA Photocatalyst for Radical Polymerization ↗Advanced Polymer Synthesis and Characterization
Abstract
Key words DNA photocatalyst - chemical stimuli - polymerization - eosin Y Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Asymmetric Enolexo-Aldol Condensations of Siladials via Enamine Catalysis ↗Asymmetric Synthesis and Catalysis
Abstract
Key words enolexo-aldol condensation - silicon stereocenter - enamine catalysis - tetraorganosilicons Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Borenium-Catalyzed Hydrogenative Cleavage of Unactivated C(Aryl)–C(Alkyl) Bonds ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Key words borenium salt - NHC ligand - hydrogenolysis - hydrocarbons Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Aminocatalytic Enantio-, Diastereo- and Periselective [4+4] Cycloaddition ↗Asymmetric Synthesis and Catalysis
Abstract
Key words thermal [4+4] cycloaddition - benzocyclooctatrienes - aminocatalysis - prolinol silyl ether Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Formal Electronically Mismatched Radical Additions ↗Radical Photochemical Reactions
Abstract
Key words radical addition - polarity transduction - olefin difunctionalization Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photocatalytic Cyclopropanation of Unactivated Olefins with α-Bromomalonates and α-Bromo-β-Keto Esters ↗Cyclopropane Reaction Mechanisms
Abstract
Key words photocatalysis - cyclopropanation - olefins - β-dicarbonyl compounds Publication History Article published online: 17 March 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Nature
Catalytic asymmetric synthesis of cannabinoids and menthol from neral ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Abstract The selective conversion of natural or synthetic neral to (1 R ,6 S )- trans -isopiperitenol would enable and expedite sustainable routes to menthol 1,2 and cannabinoids 3–5 . However, this reaction has been considered impossible because its product is more reactive to the required acid catalysts than its starting material, resulting in several side products 6–9 . We now show that an unsymmetric, strong and confined chiral acid, a highly fluorinated imino-imidodiphosphate, catalyses this process with excellent efficiency and selectivity. Expanding the method to other α,β-unsaturated aldehydes could enable access to new cannabinoids and menthol derivatives not readily accessible previously. Mechanistic studies suggest that the confined catalyst accomplishes this reaction by binding the product in an unreactive conformation, thereby preventing its decomposition. We also show how (1 R ,6 S )- trans -isopiperitenol can be readily converted to pharmaceutically useful cannabinoids and menthol, each in the shortest and most atom-economic routes so far.
2023 · The Cambridge Structural Database · dataset
CCDC 2206326: Experimental Crystal Structure Determination ↗Free copyCrystal structures of chemical compounds
Abstract
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
2023 · Journal of the American Chemical Society
Organocatalytic DYKAT of Si-Stereogenic Silanes ↗Open accessFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
High Resolution Image Download MS PowerPoint Slide Chiral organosilanes do not exist in nature and are therefore absent from the “chiral pool”. As a consequence, synthetic approaches toward enantiopure silanes, stereogenic at silicon, are rather limited. While catalytic asymmetric desymmetrization reactions of symmetric organosilicon compounds have been developed, the utilization of racemic silanes in a dynamic kinetic asymmetric transformation (DYKAT) or dynamic kinetic resolution (DKR) would significantly expand the breadth of accessible Si -stereogenic compounds. We now report a DYKAT of racemic allyl silanes enabled by strong and confined imidodiphosphorimidate (IDPi) catalysts, providing access to Si -stereogenic silyl ethers. The products of this reaction are easily converted into useful enantiopure monohydrosilanes. We propose a spectroscopically and experimentally supported mechanism involving the epimerization of a catalyst-bound intermediate.
2023 · Synfacts · editorial
Sulfonium-Based EDA Complexes Grant Access to Electronically Diverse Aryl Radicals ↗Radical Photochemical Reactions
Abstract
Key words photocatalysis - arenes - C–H functionalization - electron donor–acceptor complex Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Organocatalytic Hydrophosphonylation Towards Enantioenriched Self-Recognizing Ureidophosphonates ↗Organophosphorus compounds synthesis
Abstract
Key words hydrophosphonylation - chiral self-recognition - hydrogen bonding - heterochiral dimers - ureidophosphonates Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Radical-Based 1,4-Difunctionalization of Two Electronically Differentiated Olefins ↗Radical Photochemical Reactions
Abstract
Key words 1,4-oxyimination - energy transfer catalysis - radical chain Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Hydroalkylation of Olefins Mediated by Photochemically Generated NHC-Ligated Boryl Radicals ↗Radical Photochemical Reactions
Abstract
Key words photochemistry - boryl radicals - halogen-atom transfer - N-heterocyclic carbenes - hydroalkylation Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
A Chemo-Enzymatic Dearomatization Cascade Approach to Enantioenriched Piperidines from Pyridines ↗Enzyme Catalysis and Immobilization
Abstract
Key words amine oxidase - ene-imine reductase - chemo-enzymatic dearomatization - piperidine synthesis Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Organocatalytic/Photochemical Approach to Regioselective Functionalization of Azines ↗Radical Photochemical Reactions
Abstract
Key words dithiophosphoric acid - pyridinyl radicals - allylic radicals - azines - C–H functionalization - Minisci reaction Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Chiral Phosphoric Acid- and Photoredox-Catalyzed Enantioselective Giese Additions of α-Amino Radicals ↗Radical Photochemical Reactions
Abstract
Key words pyridines - amines - Giese addition - chiral phosphoric acid - photoredox catalysis Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Organocatalysis Enables the Isotopic Labelling of Amino Acids ↗Asymmetric Synthesis and Catalysis
Abstract
Key words aldehyde catalysis - positron emission tomography - amino acids - isotopic labelling - carbon dioxide - medical imaging Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Chiral Pyridoxal–Gold Rush in Asymmetric Carbonyl Catalysis ↗Free to readFree PDF ↗Asymmetric Synthesis and Catalysis Abstract
Key words biomimetic catalysis - C–H functionalization - carbonyl catalysis - chiral pyridoxal - β-aminoalcohols - benzylamines - squaramide Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Photocatalytic Radical Addition to N-Sulfonyl Hydrazones as a C–H Alkylation Strategy ↗Radical Photochemical Reactions
Abstract
Key words C–H alkylation - photochemistry - hydrazones - H-atom transfer Publication History Article published online: 13 February 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Angewandte Chemie International Edition
Predicting Highly Enantioselective Catalysts Using Tunable Fragment Descriptors** ↗Open accessAsymmetric Synthesis and Catalysis
Abstract
Catalyst optimization processes typically rely on inductive and qualitative assumptions of chemists based on screening data. While machine learning models using molecular properties or calculated 3D structures enable quantitative data evaluation, costly quantum chemical calculations are often required. In contrast, readily available binary fingerprint descriptors are time- and cost-efficient, but their predictive performance remains insufficient. Here, we describe a machine learning model based on fragment descriptors, which are fine-tuned for asymmetric catalysis and represent cyclic or polyaromatic hydrocarbons, enabling robust and efficient virtual screening. Using training data with only moderate selectivities, we designed theoretically and validated experimentally new catalysts showing higher selectivities in a challenging asymmetric tetrahydropyran synthesis.
2023 · Synfacts · editorial
Conformational Fixation of Organocatalyst in Metal-Organic Framework Permits Improved Enantiocontrol ↗Asymmetric Synthesis and Catalysis
Abstract
Key words imidodiphosphate (IDP) - metal-organic framework - Brønsted acid - N,N-acetalization - O,O-acetalization - asymmetric catalysis Publication History Article published online: 17 January 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
N-Heterocyclic Carbene (NHC) Catalysis Permits Diastereoselective Radical Aminoacylation of Olefins ↗N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Abstract
Key words N-heterocyclic carbene (NHC) catalysis - diastereoselectivity - aminoacylation - olefins - radical Publication History Article published online: 17 January 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany
2023 · Synfacts · editorial
Chiral Phosphoric Acid-Catalyzed Diels–Alder Reaction of 2-Trifluoroacetamido-1,3-Dienes and Enones ↗Asymmetric Synthesis and Catalysis
Abstract
Key words Diels–Alder reaction - cycloaddition - 2-amino-1,3-dienes - enones - chiral phosphoric acid Publication History Article published online: 17 January 2023 © 2023. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany