Regioselectivity Switch between Enantioselective 1,2- and 1,4-Addition of Allyl Aryl Ketones with 2,3-Dioxopyrrolidines.

Abstract

A vinylogous addition reaction of allyl aryl ketones with good yields and excellent regioselectivity catalyzed by squaramide catalysts has been developed. A series of chiral tertiary alcohols and bicyclic pyrrolidones could be synthesized in good to excellent yields, enantioselectivities, and diaseteroselectivities. Both experimental results and DFT calculations indicate that 1,2-addition reaction is favorable when the reaction is employed at a lower temperature, while the 1,4-addition/cyclization pathway is favorable when the reaction is employed at a higher temperature. Furthermore, the formation of compound 4 can potentially arise from either the 1,4-addition/cyclization pathway or retro-aldol reaction of compound 3, followed by subsequent 1,4-addition/cyclization.