Gadolinium Photocatalysis: Dearomative [2+2] Cycloaddition/Ring-Expansion Sequence with Indoles

Lanthanide photocatalysts are much less investigated in synthetic chemistry than rare and expensive late transition metals. We herein introduce Gd^III photocatalysis of a highly regioselective, intermolecular 2+2] photocycloaddition/ring-expansion sequence with indoles, which could provide divergent access to cyclopentab]indoles and indolines. A simple and commercially available Gd(OTf)₃ salt is sufficient for this visible-violet-light-induced transformation. The reaction proceeds either through a transient or start-to-end dearomatization cascade and shows excellent regioselectivity (usually >95:5 r.r.), broad scope (59 examples), good functional group tolerance and facile scale-up under mild, direct visible-light-excitation conditions. Mechanistic investigations reveal that direct excitation of the Gd(OTf)₃/indole mixture gives an excited state intermediate, which undergoes the subsequent 2+2] cycloaddition and cyclobutane-expansion cascade.