Asymmetric Catalysis of New Generation Chiral Metallosalen Complexes

Chiral metallosalen complexes have been recognized as one of the most promising catalysts for various asymmetric reactions. The studies on asymmetric epoxidation catalyzed by chiral (salen)manganese complexes will be reviewed at first. The enantioselectivities have reached to the level as high as 90—99% ee for the epoxidation of conjugated cis-di- and trisubstituted olefins by developing the second generation of chiral salen ligands. Although it has been proven by Freichtinger and Plattner that epoxidation proceeds through an oxo species, the mechanism of asymmetric induction is still surrounded by controversy. However, our recent studies have clarified that the conformation of the salen ligand in oxo(salen)manganese(V) species plays a very important role in determining the direction of the olefin’s access to the oxo species. This study led to the new finding that an achiral (salen)metal complex can be used as a chiral catalyst by regulating the conformation of achiral ligand. The appropriately modified (...