Cobalt-Catalyzed Asymmetric Migratory Nozaki-Hiyama-Kishi Coupling
Jian Chen1, Lifu Wu1, Zhiyong Song1
1State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Abstract:
Selective functionalization of ubiquitous C-H bonds based on 1,n-metal migration provides an attractive and sustainable route to access complex molecules from readily available precursors. Herein, we report a Co-catalyzed asymmetric reductive migratory Nozaki-Hiyama-Kishi (NHK) coupling between two readily available electrophiles, aryl (pseudo)halides and aldehydes, via an unprecedented through-space aryl-to-alkenyl 1,4-cobalt/hydride shift. The judicious choice of ligands is crucial for selectivity, leading to either ipso- or migratory NHK products with exquisite control of regio-, E/Z-, and enantioselectivity. Enabled by a ligand relay catalytic strategy, this platform has been further extended to aryl-to-aryl asymmetric migratory NHK coupling. These high-value NHK adducts, including α-chiral allylic alcohols and benzyl alcohols, are readily convertible to a variety of useful synthons.
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