School of Chemistry and Chemical Technology and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
J Am Chem Soc. 2012 May 16;134(19):8058-61. doi: 10.1021/ja302340b. Epub 2012 May 2.
Chiral nanoporous metal-organic frameworks are constructed by using dicarboxyl-functionalized chiral Ni(salen) and Co(salen) ligands. The Co(salen)-based framework is shown to be an efficient and recyclable heterogeneous catalyst for hydrolytic kinetic resolution (HKR) of racemic epoxides with up to 99.5% ee. The MOF structure brings Co(salen) units into a highly dense arrangement and close proximity that enhances bimetallic cooperative interactions, leading to improved catalytic activity and enantioselectivity in HKR compared with its homogeneous analogues, especially at low catalyst/substrate ratios.
手性纳米多孔金属有机骨架是通过使用二羧酸官能化的手性 Ni(salen)和 Co(salen)配体制备的。研究表明,基于 Co(salen)的骨架是一种高效且可回收的非均相催化剂,可用于外消旋环氧化物的水解动力学拆分(HKR),对映体过量值高达 99.5%。MOF 结构使 Co(salen)单元形成高度密集的排列和紧密相邻,从而增强了双金属协同相互作用,与均相类似物相比,在 HKR 中提高了催化活性和对映选择性,特别是在低催化剂/底物比的情况下。