Novel Stereo‐Induction Pattern in Pudovik Addition/Phospha‐Brook Rearrangement Towards Chiral Trisubstituted Allenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 23, 2024

Abstract Despite the significance of chiral allene skeletons in catalysis, organic synthesis and medicinal chemistry et al., there is a scarcity reports on axially allenyl phosphorus compounds. Here, we disclosed an efficient straightforward cascade reaction between ethynyl ketones phosphine oxides, resulting broad array trisubstituted allenes incorporating moiety high yields with excellent stereoselectivities facilitated by peptide‐mimic phosphonium salt (PPS) Additionally, comprehensive series mechanistic experiments have been conducted to elucidate that this proceeds via asymmetric Pudovik addition followed subsequent phospha ‐Brook rearrangement occurs concomitantly kinetic resolution, representing stereospecific protonation process facilitating central‐to‐axial chirality transfer manner. We anticipate our research will pave way for promising exploration novel stereo‐induction pattern addition/ reaction.

Language: Английский

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Design and Application of Peptide‐Mimic Phosphonium Salt Catalysts in Asymmetric Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: July 6, 2023

Chiral phosphonium salt catalysis, traditionally classified as a type of phase transfer has proven to be powerful strategy for the stereoselective preparation diverse optically active molecules. However, there still remain numerous forbidding issues reactivity and selectivity in such well-known organocatalysis system. Accordingly, development new high-performance catalysts with unique chiral backbones is highly desirable, yet challenging. This Minireview describes prominent endeavours family peptide-mimic multiple hydrogen-bonding donors their applications plethora enantioselective synthesis during past few years. Hopefully, this minireview will pave way further developing much more efficient privileged ligands/catalysts featuring exclusively catalytic ability asymmetric synthesis.

Language: Английский

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Organocatalytic skeletal reorganization for enantioselective synthesis of S-stereogenic sulfinamides

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 22, 2024

Abstract The enantioselective synthesis of S -stereogenic sulfinamides has garnered considerable attention due to their structural and physicochemical properties. However, catalytic asymmetric still remains daunting challenges, impeding broad application in drug discovery development. Here, we present an approach for the through peptide-mimic phosphonium salt-catalyzed skeletal reorganization simple prochiral and/or racemic sulfoximines. This methodology allows facile access a diverse array substituted with excellent enantioselectivities, accommodating various substituent patterns desymmetrization or parallel kinetic resolution process. Mechanistic experiments, coupled density functional theory calculations, clarify stepwise pathway involving ring-opening ring-closing processes, step identified as crucial achieving stereoselective control. Given prevalence centers pharmaceuticals, anticipate that this protocol will enhance efficient precise relevant chiral molecules analogs, thereby contributing advancements discovery.

Language: Английский

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Enantioselective Synthesis of Atropisomeric Biaryl Phosphorus Compounds by Chiral‐Phosphonium‐Salt‐Enabled Cascade Arene Formation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(30)

Published: May 12, 2022

Axially chiral biaryl monophosphorus molecules, exemplified by atropisomeric 1,1'-biaryl aminophosphines, are significant motifs in numerous ligands/catalysts. Developing efficient methods for preparing phosphorus compounds with these privileged is an important endeavor synthetic chemistry. Herein, we develop effective, modular method a chiral-phosphonium-salt-catalyzed novel cascade between phosphorus-containing nitroolefins and α,α-dicyanoolefins, leading to great diversity of biaryls bearing groups high yields excellent stereoselectivities. The reaction features include Thorpe-type cycloaddition/oxidative hydroxylation/aromatization pathway central-to-axial chirality transfer process. Insight gained from our studies expected advance general efforts towards the catalytic synthesis compounds, offering platform developing new ligands catalysts.

Language: Английский

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Synergistic Catalysis between a Dipeptide Phosphonium Salt and a Metal‐Based Lewis Acid for Asymmetric Synthesis ofN‐Bridged [3.2.1] Ring Systems

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 29, 2022

Abstract We present an unprecedented synergic catalytic route for the asymmetric construction of fluorinated N ‐bridged [3.2.1] cyclic members tropane family via a bifunctional phosphonium salt/silver co‐catalyzed cyclization process. A broad variety substrates bearing assortment functional groups are compatible with this method, providing targeted compounds seven‐membered ring and four contiguous stereocenters in high yields excellent stereoselectivities. The gram‐scale preparations, facile elaborations preliminary biological activities products demonstrate application potential. Moreover, both experimental computational mechanistic studies revealed that proceeded “sandwich” reaction model multiple weak‐bond cooperative activations. Insights gained from our expected to advance general efforts towards synthesis challenging chiral heterocyclic molecules.

Language: Английский

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A Stereospecific Alkene 1,2‐Aminofunctionalization Platform for the Assembly of Complex Nitrogen‐Containing Ring Systems

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 22, 2023

TFA promoted deprotection of O-Ts activated N-Boc hydroxylamines triggers aminofunctionalization-based polycyclizations tethered alkenes. The processes involve intramolecular stereospecific aza-Prilezhaev alkene aziridination in advance C-N cleavage by a pendant nucleophile. Using this approach, wide range fully anti-1,2-difunctionalizations can be achieved, including diaminations, amino-oxygenations and amino-arylations. Trends associated with the regioselectivity step are outlined. method provides broad predictable platform for accessing diverse C(sp3 )-rich polyheterocycles relevance to medicinal chemistry.

Language: Английский

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Enantioselective Synthesis of Atropisomers by Oxidative Aromatization with Central-to-Axial Conversion of Chirality

Molecules, Journal Year: 2023, Volume and Issue: 28(7), P. 3142 - 3142

Published: March 31, 2023

Atropisomers are fascinating objects of study by themselves for chemists but also find applications in various sub-fields applied chemistry. Obtaining them enantiopure form is far from being a solved challenge, and the past decades has seen surge methodological developments that direction. Among these strategies, oxidative aromatization with central-to-axial conversion chirality gained increasing popularity. It consists oxidation cyclic non-aromatic precursors into corresponding aromatic atropisomers. This review proposes critical analysis this research field delineating it discussing its historical background present state art to draw potential future development directions.

Language: Английский

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Advances in Catalytic Asymmetric Reactions Involving o-Hydroxyphenyl Substituted p-Quinone Methides^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(7), P. 793 - 793

Published: Jan. 1, 2023

o-Hydroxyphenyl substituted p-quinone methides (p-QMs) belong to a class of p-QMs with unique advantages.They not only maintain the high reactivity p-QMs, but also have more reactive and activation sites owing introduction hydroxyl group.Therefore, o-hydroxyphenyl wide applications in synthetic medicinal chemistry.The catalytic asymmetric 1,6-conjugate addition [4＋n] cycloaddition developed very rapidly recent years, which become efficient strategies for synthesis chiral oxygen-containing heterocycles arylmethanes potential bioactivity.This review summarizes reactions involving points out remaining challenges this research area, will open new window design type their involved reactions.

Language: Английский

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Chiral Isothiourea‐Catalyzed Acylative Dynamic Kinetic Resolution of 3‐Hydroxyphthalides for Enantioselective Synthesis of Phthalidyl Esters

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(19), P. 2341 - 2345

Published: May 27, 2024

Comprehensive Summary Phthalides serve as core structures pervasive in a wide array of natural products and drug molecules, which display diverse biological activities. We report herein highly efficient dynamic kinetic resolution 3‐hydroxyphthalides by chiral isothioureas (ITUs) catalyzed asymmetric acylation, facilitating the effective synthesis variety phthalidyl esters with good yields enantioselectivities. Notably, this reaction features mild conditions, expansive substrate scope well functional group compatibility. In addition, practicality method is underscored large‐scale synthesis, reduced catalyst loading experiment ester prodrug.

Language: Английский

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An efficient and environmentally benign domino protocol for the synthesis of spirodihydropyridines using europium-doped ZnO nanoparticles as recyclable and reusable heterogeneous catalyst

Research on Chemical Intermediates, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

Language: Английский

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