Umpolung Reaction of α-Imino Thioesters and the Subsequent C-C Bond Formation with the Unexpected Alkylthio Rearrangement.

An umpolung reaction of the α-imino thioester was examined, and we found that α-imino thioesters were more effective substrates for the umpolung N-alkylation than conventional α-imino esters and they gave N-alkylated amino thioesters in high yields under mild reaction conditions in a short time. A new type of C-C bond formation followed by an unexpected rearrangement of the alkylthio group took place with the unsaturated ketones to afford the β-alkylthio-α-amino thioesters in high yields with good diastereoselectivity.