Propargyl Alcohols as Bifunctional Reagents for Divergent Annulations of Biphenylamines via Dual C-H Functionalization/Dual Oxidative Cyclization.

The C-H functionalization strategy provides access to valuable molecules that previously required convoluted synthetic attempts. Dual C-H unsymmetrical functionalization, with a single bifunctional reagent, is an effective tactic. Propargyl alcohols (PAs), despite containing a reactive C≡C bond, have not been explored as building blocks via oxidative cleavage. Annulations via C-H activation are a versatile and synthetically attractive strategy. We disclose PA as a new bifunctional reagent for unsymmetrical dual C-H functionalization of biphenylamine for regioselectively annulated outcomes. On tuning the conditions, the annulation bifurcated towards an unusual dual oxidative cyclization. This method accommodates a wide range of PAs and showcases late-stage diversification of some natural products.