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

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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

Язык: Английский

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

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 7741 - 7748

Опубликована: Апрель 25, 2025

Язык: Английский

Nickel-Catalyzed Reductive 1,4-Alkylacylation of 1,3-Enynes Enabling Synthesis of Allenyl Ketones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

A nickel-catalyzed reductive 1,4-alkylacylation of 1,3-enynes has been established using nonactivated tertiary alkyl bromides and aromatic anhydrides as dual electrophiles. This protocol enables efficient assembly tetrasubstituted allenyl ketones with high chemo- regioselectivity. Mechanistic insights reveal the radical relay process involving synergistic interactions nickel zinc. The ketone products serve modular building blocks, particularly for constructing fully carbon-substituted furans via Au-catalyzed cycloisomerization selective 1,2-aryl migration, enhancing synthetic practicality.

Язык: Английский