A General Three-Component Nozaki–Hiyama–Kishi-Type Reaction Enabled by Delayed Radical-Polar Crossover

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Nozaki–Hiyama–Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, application multicomponent NHK-type reactions, which allow multiple bonds in single step, has been largely restricted to bulky alkyl precursors, thus limiting their expanded utilization. Herein, we disclose general three-component reaction enabled by delayed crossover, efficiently tolerates plethora precursors that were previously unavailable. This method enables modular assembly versatile homoallylic alcohols feedstock chemicals with excellent chemo-, regio-, diastereo-, and enantioselectivities step. Experimental studies density functional theory (DFT) calculations reveal kinetically favored an allylchromium(III) species is paramount enforcing crossover over direct addition. Finally, straightforward transformations applications products demonstrated, showcasing synthetic utility this method.

Language: Английский

Photoexcited Hantzsch Ester and Cobalt Catalysis Enable Diastereo- and Enantioselective Allylation of Aldehydes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6165 - 6172

Published: April 2, 2025

Language: Английский