Chiral salen ligands designed to form polymetallic complexes

Chiral salen ligands capable of forming polymetallic complexes have been designed. The ligands possess substituents in the 4,4'-positions, but have no substituent in the 3,3'-positions to allow a second metal ion access to the salen oxygen atoms. Ligands in which a polyether chain links the 4,4'-positions were prepared and complexed to copper. In addition, acyclic ligands with potential metal coordinating substituents in the 4,4'-positions were prepared and complexed to copper and cobalt. The crystal structure of one of the cobalt complexes shows it to be a trimetallic complex in which a Co(II)(OAc)(2) group coordinates to the salen oxygen atoms of two Co(Ill)(salen)(OAc) units. In contrast, the crystal structure of a Co(salen) complex with tert-butyl groups attached to the 3,3'-positions is found to be mononuclear. All of the complexes were tested as asymmetric phase transfer catalysts for the asymmetric alkylation of an alanine methyl ester, forming (R)-alpha-methyl phenylalanine methyl ester with up to 85% ee. (C) 2011 Elsevier Ltd. All rights reserved.