Catalyst-Controlled C-H Functionalization of Adamantanes Using Selective H-Atom Transfer

A method for the direct functionalization of diamondoids has been developed using photoredox and H atom transfer catalysis. This C-H alkylation reaction has excellent chemoselectivity for the strong 3 degrees C-H bonds of adamantanes in polyfunctional molecules. In substrate competition reactions, a reversal in selectivity is observed for the new H-atom transfer catalyst reported here in comparison to five known photo-chemical systems. Derivatization of a broad scope of diamondoids and adamantane-containing drugs highlights the versatility and functional group tolerance of this C-H functionalization strategy.