Asymmetric isomerization of ω-hydroxy-α,β-unsaturated thioesters into β-mercaptolactones by a bifunctional aminothiourea catalyst.

We present a novel methodology for the asymmetric synthesis of β-mercaptolactones via isomerization of ω-hydroxy-α,β-unsaturated thioesters by means of a bifunctional aminothiourea catalyst. The catalyst interacts with the substrate through the cooperative action of both a covalent bond at the amino group and noncovalent bonding at the thiourea group. The potential for an enantiodivergent synthesis could also be demonstrated by carrying out the reaction in a different solvent system.