Transition‐Metal‐Free Ring‐Opening Silylation of Indoles and Benzofurans with (Diphenyl‐<i>tert</i>‐butylsilyl)lithium

Abstract

A practical method is presented for ring opening various indoles and benzofurans with concomitant stereoselective silylation using readily generated (diphenyl-tert-butylsilyl)lithium to afford ortho-β-silylvinylanilines or -phenols. Dearomatization of the heteroarene core proceeds in the absence of any transition-metal catalyst through addition of a silyl anion and a subsequent stereoselective β-elimination. DFT calculations provide insight into the mechanism. Functionalizing C-X bond cleavage of heteroarenes is rare and generally requires transition-metal catalysts.