Rh(III)-Catalyzed Csp2-Csp3 Bond Alkoxylation of alpha-Indolyl Alcohols via C-C sigma Bond Cleavage

A Rh(III)-catalyzed direct Csp2–Csp3 bond alkoxylation of α-(2-indolyl)alcohols with alcohols has been reported. This transformation features a rapid C–C sigma bond/C–O single bond switch, and provides a novel approach for assembling 2-alkoxylindole skeletons. A catalytic cycle involving a β-aryl elimination process is proposed.