2002 年 60 巻 8 号 p. 752-761
Planar chiral cyclopentadienyl complexes of late transition metals were synthesized by using trisubstituted cyclopentadienes. Each enantiomer has been isolated as an optically pure form by fractional recrystallization of (l) -menthyl ester derivatives followed by the removal of the (l) -men-thyl group. Cyclopentadienyl ruthenium complexes possessing an anchor phosphine ligand, which prevents the rotation of the cyclopentadienyl ring, were also prepared. The planar-chiral ruthenium complexes showed high diastereoselectivity in some reactions such as complexation of dienes and substitution with phosphines. The planar-chiral ruthenium complexes with anchor phosphine ligands were successfully applied to asymmetric allylic amination and alkylation. In these reac-tions, the anchor phosphine ligand acts as an important role to control the stereochemistry of the products.