Ring-opening silylation of N-arylindoles via endocyclic C–N bond cleavage triggered by silylboranes

The cleavage of heteroaromatic endocyclic carbon-heteroatom bonds to assemble C-Si bonds is scarce. Here, we demonstrate an unprecedented dearomatization silylation of N-arylindoles arising from reductive activation initiated by electron-rich silylboronic complexes to deliver silyl styrenes with perfect stereoselectivity.