Diastereoselective Aldol Reaction of α-Azido Ketones with α-CF₃ Pyruvate to Organoazides with Vicinal Tetrasubstituted Carbons

A direct diastereoselective aldol reaction of cyclic or acyclic α-azido ketones with α-trifluoromethyl (CF₃) pyruvate catalysed by DABCO is developed, which allowed the facile access of CF₃-containing multifunctional organoazides with vicinal tetrasubstituted carbons in good to high yields and diastereoselectivities. Moreover, phenylethynyl trifluoro- and difluoromethyl ketones are also viable substrates. Up to 50 % enantioselectivity could be obtained in the initial exploration of the catalytic asymmetric variant.