Phosphine Oxide-Catalyzed Asymmetric Aldol Reactions and Double Aldol Reactions

Abstract

Chiral phosphine oxides successfully catalyze asymmetric cross-aldol reactions of various carbonyl compounds in a highly enantioselective manner. The phosphine oxide catalysts coordinate to chlorosilanes to form chiral hypervalent silicon complexes in situ, which activate both aldol donors and acceptors, thus realizing cross-aldol reactions between a ketone and an aldehyde, between two aldehydes, between two ketones, and of 2,6-diketones. The use of phosphine oxide catalysis can be further extended to achieve the first catalytic enantioselective double aldol reactions, realizing one-pot stereoselective construction of up to four stereogenic centers.

Keywords: aldol reaction; hypervalent silicon complex; phosphine oxide; sequential activation; stereoselective; tandem catalysis.