Enhanced cooperativity through design: Pendant Co-III-salen polymer brush catalysts for the hydrolytic kinetic resolution of epichlorohydrin (salen = N,N '-bis(salicylidene)ethylenediamine dianion)

摘要

The Co-III-salen-catalyzed (salen = N,N'-bis(salicylidene)ethylenediamine dianion) hydrolytic kinetic resolution (HKR) of racemic epoxides has emerged as a highly attractive and efficient method of synthesizing chiral C-3 building blocks for intermediates in larger, more complex molecules. HKR reaction rates have displayed a second order dependency on the concentration of active sites, and thus researchers have proposed a bimetallic transition state for the HKR mechanism. Here we report the utilization of pendant Co-III-salen catalysts on silica supported polymer brushes as a catalyst for the HKR of epichlorohydrin. ne novel polymer brush architecture provided a unique framework for promoting site-site interactions as required in the proposed bimetallic transition state of the HKR mechanism. Furthermore, the polymer brushes mimic the environment of soluble polymer-based catalysts, whereas the silica support permitted facile recovery and reuse of the catalyst. The polymer brush catalyst displayed increased activities over the soluble Jacobsen Co-salen catalyst and was observed to retain its high enantioselectivities (> 99%) after each of five reactions despite decreasing activities. Analysis indicated decomposition of the salen ligand as an underlying cause of catalyst deactivation.