American Chemical Society
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Photoredox-Catalyzed Three-Component 1,2-Cyanoalkylpyridylation of Styrenes with Nonredox-Active Cyclic Oximes

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journal contribution
posted on 2023-11-09, 14:00 authored by Rui Liu, Ting Zou, Sha Yu, Weicai Li, Siping Wei, Yimou Gong, Zhijie Zhang, Shiqi Zhang, Dong Yi
Three-component alkene 1,2-difunctionalizations have emerged as a powerful strategy for rapid buildup of diverse and complex alkylpyridines, but the distal functionalized alkyl radicals for the alkene 1,2-alkylpyridylations were still rare. Herein, we report an example of regioselective three-component 1,2-cyanoalkylpyridylation of feedstock styrenes with accessible nonredox-active cyclic oximes through visible-light photoredox catalysis, providing a series of structurally diverse β-cyanoalkylated alkylpyridines. This protocol proceeds through a radical relay pathway including the generation of iminyl radicals enabled by phosphoranyl radical-mediated β-scission, radical transposition through C–C bond cleavage, highly selective radical addition, and precise radical–radical cross-coupling sequence, thus facilitating the regioselective formation of two distinct C–C single bonds in a single-pot operation. This synthetic strategy features mild conditions, broad compatibility of functional groups and substrate scope, diverse product derivatization, and late-stage modification.