Participation of an organosulfur functionality in asymmetric Pauson–Khand reactions using (S)-methionine-derived amides as enantiocontrollable substrates

An asymmetric Pauson–Khand reaction was successfully accomplished using chiral phenylpropiolic carboxamides derived from (S)-methionine. Participation of the organosulfur functionality with cobalt catalysts in the asymmetric Pauson–Khand reaction is clearly demonstrated, giving the corresponding Pauson–Khand reaction products with extremely high diastereoselectivity in comparison to other substrates without similar sulfenyl groups. The absolute configuration of the newly created chiral carbon centers was determined by X-ray crystallographic analysis. The mechanism for the asymmetric induction is proposed on the basis of the stereochemistry of the reactions determined by us.