Phosphine-Catalyzed Asymmetric Umpolung Addition of Trifluoromethyl Ketimines to Morita-Baylis-Hillman Carbonates

A novel phosphine‐catalyzed, highly enantioselective umpolung addition of trifluoromethyl ketimines to Morita–Baylis–Hillman carbonates was developed and it provides facile access to optically active trifluoromethyl amines with a chiral tertiary stereocenter under mild reaction conditions. The salient features of this reaction include general substrate scope, mild reaction conditions, good yields, high enantioselectivity, ease of scale‐up to gram scale, and further transformations of the products. Flip flop: The title reaction provides facile access to optically active trifluoromethyl amines with a tertiary stereocenter under mild reaction conditions. The salient features of this reaction include a general substrate scope, good yields, and high enantioselectivities. Boc=tert‐butoxycarbonyl.