Carbocation versus carbene controlled chemoselectivity: Dft study on gold- And silver-catalyzed alkylation/cyclopropanation of indoles with vinyl diazoesters

Density functional theory calculations were performed to investigate the catalyst-controlled selective functionalization of indoles with vinyl diazoacetates. The detailed reaction mechanism was established, and different roles of carboncation or carbene intermediates in defining an experimentally observed chemo- and regioselectivity were fully rationalized. © 2020 American Chemical Society.