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

Copper-Catalyzed Enantioselective Radical Cyanation of Allenic C(sp²)–H Bonds to Access Tri- and Tetrasubstituted Chiral Allenes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7741 - 7748

Published: April 25, 2025

Language: Английский