Our recent studies on asymmetric synthesis with the assistance of organomet
al catalysts stereocontrolled by organosulfur functionality involved in rea
ction substrates or ligands are reviewed. The studies focused on asymmetric
synthesis via chiral pi-allylmetal complexes derived from (S)-proline ally
l ester, olefinic cyclopropanes, chiral 2-alkynyl sulfinates, and chiral ne
w ligands, and also focused on asymmetric cycloaddition reactions with chir
al sulfoxides and sulfinates, such as intramolecular ene, metallo-type ene,
and hetero Diels-Alder reactions. Participation of organosulfur functional
ity in organometal-catalyzed asymmetric reactions was unveiled on the basis
of the stereochemical outcomes obtained.