Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

Abstract

Herein we report a nickel-catalyzed asymmetric two-component reductive aryl-acylation and arylcarbamoylation of aryl-iodide-tethered unactivated alkenes, which utilize ortho-pyridinyl esters and isocyanates as the electrophilic acyl sources, respectively. Under the catalysis of a nickel-pyrox complex with zinc powder as the reductant, a variety of chiral indanes, indolines, and dihydrobenzofurans bearing a quaternary stereogenic center were prepared in moderate to high efficiency and good to excellent enantioselectivities. The utility of this method is demonstrated by various simple derivatizations of the attached carbonyl group, particularly the sequential benzylic oxidation and pinacol coupling, which provide a concise entry to the benzene-fused bicyclic bridged ring framework containing three challenging tetrasubstituted stereocenters in high stereocontrol.