Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

ConspectusIn recent years, radical-mediated cross-coupling reactions have emerged as a compelling strategy for achieving rich diversity in molecular topologies under benign conditions. However, the inherent high reactivity of radicals presents considerable challenges controlling reaction pathways and selectivity, which often results limited range substrates constrained profile. Given capacity visible-light photoredox catalysis to generate wide variety reactive radical ions controlled manner propensity copper complexes toward species, we envisaged that synergy between chiral catalysts photoactive would pave way developing innovative strategies. This integration is poised unlock broad spectrum enantioselective multicomponent reactions.In this Account, describe our insights efforts realm reactions. These advancements been achieved through application dual photoredox/copper or bifunctional visible light irradiation. Our work systematically divided into two sections based on activation modes. The first section focuses photoinduced copper-catalyzed C-C C-O bond formation addition/nucleophilic trap sequence. discussion particularly concentrated asymmetric carbocyanation carboarylation vinylarenes, 1,3-enynes, 1,3-dienes. findings underscore irradiation with can adeptly modulate pace generation, thus orchestrating consecutive stages ensuring attainment both chemo- stereoselectivity. In domain formation, leveraging carboxylic acids nucleophilic oxygen source, introduce suite esterification benzylic, allylic, propargylic radicals. are derived from precursors, showcasing versatility approach. following highlights discovery field catalysis, enables three-component transformations via direct aromatic alkenes. methodology begins generation formal distonic anions photocatalytic single-electron reduction alkenes, thus, enabling orthogonal reactivity. Employing H

Language: Английский

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Dual Photoredox- and Titanium Catalysis-Enabled Three-Component Radical Propargylation of Aldehydes with 1,3-Enynes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Herein, a straightforward and practical strategy involving radicals for the three-component carbonyl propargylation via dual photoredox titanium catalysis is presented. This delivers homopropargyl alcohols includes readily available starting materials, broad substrate scope, high functional group tolerance, mild reaction conditions. Catalytic Cp2TiCl2, recognized as an inexpensive, nontoxic, bench-stable source, employed.

Language: Английский

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Cu-Catalyzed Asymmetric Three-Component Radical Acylarylation of Vinylarenes with Aldehydes and Aryl Boronic Acids

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32235 - 32242

Published: Nov. 13, 2024

The direct use of readily available aldehydes as acyl radical precursors has facilitated diverse three-component acylative difunctionalization reactions alkenes, offering a powerful route to synthesize β-branched ketones. However, asymmetric alkenes with still remains elusive. Here we report copper-catalyzed acylarylation vinylarenes and aryl boronic acids. This method begins formation from an aldehyde via hydrogen atom transfer. adds the alkene, forming new benzylic that then undergoes enantioselective arylation. A chiral binaphthyl-tethered bisoxazoline ligand is essential for achieving high stereocontrol. strategy enables synthesis range synthetically valuable β,β-diaryl ketones vinylarenes.

Language: Английский

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Photoinduced Copper‐Catalyzed Three‐Component Radical Carboamination of Styrene Derivatives

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(23)

Published: Aug. 28, 2024

Abstract The catalytic three‐component radical carboamination of alkenes has recently emerged as an alternative and robust platform for the rapid construction diverse valuable amines. Despite great advances in this field, new methods that enable highly selective access to chemical space surrounding amine functional groups are still high demand. Herein, we report a generally applicable visible light‐induced copper‐catalyzed cyanoalkylamination reaction alkenes, oxime carbonates, benzoyloxycarbamates. This protocol demonstrates chemo‐selectivity, broad substrate scope, good group tolerance, providing variety cyanoalkylated aliphatic amines with yields.

Language: Английский

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