Decarboxylative Organocatalyzed Aldol-Type Addition Reaction of Chloroacetate Surrogates.

Chlorinated malonic acid half thioesters were established as chloroacetate surrogates and used in stereoselective organocatalyzed decarboxylative aldol-type additions. Enantioenriched α-chloro-β-hydroxy thioesters were obtained under mild reaction conditions in high yields and allowed for diverse derivatization as highlighted by the synthesis of (+)-prebalamide and (+)-norbalasubramide analogs.