Nickel/Photoredox Dual-Catalyzed Migratory Reductive C(sp2)-H/Si-Cl Cross-Coupling
Kailin Yin1, Yuhang Wang1, Dongbing Zhao1
1State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, China.
Abstract:
Organosilicon compounds have been extensively utilized in both industry and academia. Transition metal-catalyzed migratory cross-coupling involving 1,n-metal migration allows functionalization of C-H bonds on a remote site that are otherwise difficult to achieve. However, until now, forging C-Si bond via migratory cross-coupling seems to have not been presented. Herein, we report a nickel/photoredox dual-catalyzed migratory cross-coupling that enables the first formal remote C(sp2)-H silylation with chlorosilanes, thus achieving site-selective ipso/ortho-difunctionalization of readily available aryl bromides. The protocol proceeds under visible-light irradiation without stoichiometric metallic reductants and delivers a broad array of multisubstituted arylsilanes with excellent chemo-, regio-, and E/Z-selectivity. The synthetic utility of the method is further demonstrated through diverse downstream transformations and the preparation of silicon-containing polymers, highlighting its potential in complex molecule synthesis and materials chemistry.
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