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手性纳米多孔金属-金属席夫碱配合物用于环氧化物的水解动力学拆分。

Chiral nanoporous metal-metallosalen frameworks for hydrolytic kinetic resolution of epoxides.

机构信息

School of Chemistry and Chemical Technology and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.

出版信息

J Am Chem Soc. 2012 May 16;134(19):8058-61. doi: 10.1021/ja302340b. Epub 2012 May 2.

Abstract

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.

摘要

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。

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