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 (CF 3 ) pyruvate catalysed by DABCO is developed, which allowed the facile access of CF 3 ‐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.