title: Functionalized Metal-Organic Framework as a Biomimetic Heterogeneous Catalyst for Transfer Hydrogenation of Imines.
abstract: Mimicking a biocatalytic system has been one of the prevalent strategies for the design of novel and efficient chemical transformations. Among the enzyme-catalyzed reactions, the cooperative interplay of Lewis- and Brønsted-acidic functionalities at active sites represents a common feature in activating reactants. Employing MIL-101(Cr) as a biomimetic platform, we customize a sulfonic group (SO3H) into its hierarchical pores to generate a heterogeneous catalyst for transfer hydrogenation of imines by using Hantzsch ester as the reductant. Both aldimines and ketimines were efficiently converted to their hydrogenated counterparts in a manner similar to metal enzymes. The Cr3+node and sulfonic acid functionality encapsulated in MOF cages worked cooperatively in promoting this transformation, resulting in an enhanced reactivity as compared to its homogeneous analogue. Furthermore, MIL-101(Cr)-SO3H could be recycled for many times without considerable loss in reactivity.
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Jingwen
authors.initials: J
authors.lastname: Chen
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Zhiguo
authors.identifier: http://orcid.org/0000-0003-1681-4853
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Zongbi
authors.initials: Z
authors.lastname: Bao
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Ye
authors.initials: Y
authors.lastname: Su
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Huabin
authors.initials: H
authors.lastname: Xing
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Qiwei
authors.identifier: http://orcid.org/0000-0002-6469-5126
authors.initials: Q
authors.lastname: Yang
authors.affiliation: Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University , Zheda Road 38, Hangzhou 310027, China.
authors.forename: Qilong
authors.initials: Q
authors.lastname: Ren
keywords: Brønsted acid; Hantzsch ester; biomimetic catalyst; hydrogenation; imine; metal−organic frameworks