Acylation of Electron-Poor Alkenyl Sulfoxides: Diverse Transformations for the Synthesis of Polysubstituted Phenols and Functionalized Carbocycles

Synthesis, Journal Year: 2023, Volume and Issue: 55(17), P. 2674 - 2682

Published: May 15, 2023

Abstract A protocol with available starting materials and mild conditions was developed for the synthesis of polysubstituted phenols functionalized carbocycles via acylation electron-poor alkenyl sulfoxides. The plausible mechanism investigated.

Language: Английский

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Metal-Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends.

Published: Nov. 3, 2020

<p>Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types reactions, catalysts dissociate. Our results corroborate past studies where free mechanisms proposed be operative. Calculations on case predict that the origin metal-catalyst ‘falling off’ (dissociation) can attributed primarily steric bulkiness groups adjacent carbene carbon. </p>

Language: Английский

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Chemoenzymatic Cascades for the Enantioselective Synthesis of β‐Hydroxysulfides Bearing a Stereocentre at the C−O or C−S Bond by Ketoreductases

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(31)

Published: May 16, 2022

Abstract Chiral β‐hydroxysulfides are an important class of organic compounds which find broad application in and pharmaceutical chemistry. Herein we describe the development novel biocatalytic chemoenzymatic methods for enantioselective synthesis by exploiting ketoreductase (KRED) enzymes. Four KREDs were discovered from a pool 384 enzymes identified isolated through metagenomic approach. KRED311 KRED349 catalysed bearing stereocentre at C−O bond with opposite absolute configurations excellent ee values biocatalytic‐chemical‐biocatalytic (bio‐chem‐bio) cascades starting commercially available thiophenols/thiols α‐haloketones/alcohols. KRED253 KRED384 C−S enantioselectivities dynamic kinetic resolution (DKR) racemic α‐thioaldehydes.

Language: Английский

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Reactions of Ylides Generated from M C Bonds

Elsevier eBooks, Journal Year: 2021, Volume and Issue: unknown, P. 221 - 264

Published: Nov. 25, 2021

Language: Английский

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