Enantioselective Alkynylation Of Trifluoromethyl Ketones Catalyzed By Cation-Binding Salen Nickel Complexes

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 chemo-selectivity 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 (K-a=6.6x10(5) m(-1)).