Organocatalytic Enantioselective Decarboxylative Addition of Malonic Half Thioesters to Imines

We describe a biomimetic organocatalytic enantioselective decarboxylative addition of malonic acid half thioesters to imines. This simple protocol makes use of readily available Cinchona-derived organocatalysts and nucleophiles at the carboxylate oxidation state. The resulting beta-amino thioesters, being attractive precursors for the preparation of optically active beta-amino acids, are formed in good yields and in up to 79% ee. As suggested by several mechanistic insights the desired products are formed via initial formation of a thioester acetate enolate via decarboxylation of the malonic acid half thioester, followed by addition to the imine.