Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation‐Binding Salen Nickel Complexes

Abstract

Cation-binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99%) and high enantioselectivity (up to 97% ee). The reaction proceeds with substoichiometric quantities of base (10–20 mol% KOt-Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemoselectivity was observed, generating 1,2-addition products exclusively over 1,4-addition products. UV-vis analysis revealed the pendant oligo-ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (Ka = 6.6 105m1 ).