Nickel-Catalyzed Synthesis of Silaindanes via Sequential C–H Activating 1,5-Nickel Migration and C–Si Activating 1,4-Nickel Migration

Abstract

Catalytic reactions involving 1,n-metal migration provide a powerful approach for the synthesis of complex molecular skeletons from simple precursors through the activation of unreactive bonds. In this work, a nickel-catalyzed synthesis of 3,3-disubstituted 1-silaindanes, silicon analogues of valuable indanes, was developed by the reaction involving 1,5-nickel migration via C–H bond activation and 1,4-nickel migration via C–Si bond activation. It was found that 1,5-nickel migration not only enabled the C–H bond activation at a remote position but also controlled the regioselectivity of subsequent alkene insertion. The detailed reaction mechanism was investigated by conducting deuterium labeling experiments and DFT calculations. The results obtained here demonstrate the high potential of catalytic reactions involving nickel migrations via C–H and C–Si bond activations for the synthesis of useful cyclic organosilicon compounds.