Self-Assembly Approach toward Chiral Bimetallic Catalysts: Bis-Urea-Functionalized (Salen)Cobalt Complexes for the Hydrolytic Kinetic Resolution of Epoxides

A series of novel bis-urea-functionalized (salen)Co complexes has been developed. The complexes were designed to form self-assembled structures in solution through intermolecular urea urea hydrogen-bonding interactions. These bis-urea (salen)Co catalysts resulted in rate acceleration (up to 13 times) in the hydrolytic kinetic resolution (HKR) of rac-epichlorohydrin in THF by facilitating cooperative activation, compared to the monomeric catalyst. In addition, one of the bis-urea (salen)Co-III catalyst efficiently resolves various terminal epoxides even under solvent-free conditions by requiring much shorter reaction time at low catalyst loading (0.03-0.05 mol To). A series of kinetic/mechanistic studies demonstrated that the self-association of two (salen)Co units through urea urea hydrogen bonds was responsible for the observed rate acceleration. The self-assembly study with the his-urea (salen)Co by FTIR spectroscopy and with the corresponding (salen)Ni complex by H-1 NMR spectroscopy showed that intermolecular hydrogen-bonding interactions exist between the his-urea scaffolds in THF. This result demonstrates that self-assembly approach by using non-covalent interactions can be an alternative and useful strategy toward the efficient HKR catalysis.