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 (salen)manganese(III) complexes can also be applicable for asymmetric oxidation of enol ether derivatives, kinetic resolution of racemic allenes, enantioselective benzylic C-H oxidation, asymmetric desymmetrization of meso- heterocycles, and asymmetric oxidation of alkyl aryl sulfides. In the asymmetric aziridination of styrene derivatives by using PhI=NTs as a terminal oxidant, high enantioselectivity of up to 94% has been achieved by the further modification of the chiral (salen)manganese(III) complex. The chiral (salen)cobalt-(III) complex is a good catalyst for asymmetric cyclopropanation of styrene derivatives and asymmetric S-ylide formation from allyl aryl sulfides, in which the resulting S-ylides undergo [2,3]-Wittig rearrangement in situ to produce chiral 2-(phenylthio)pentanoate derivatives.
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