Borane-Catalyzed Enantioselective α-Alkylation of Unactivated 2-Alkylbenzoxazoles with Electron-Deficient Olefins

Chiral borane-catalyzed reactions have recently emerged as a powerful tool for the enantioselective production of chiral scaffolds. In this study, we demonstrated for the first time that a chiral bisborane catalyst can be used for the alpha-functionalization of 2-alkylazaarenes; specifically, we accomplished unprecedented highly enantioselective alpha-alkylation of unactivated 2-alkylbenzoxazoles with electron-deficient olefins. The strong Lewis acidity and the steric bulk of the bisborane catalyst were essential to the observed reactivity and selectivity.