Zhang Yin, Chen Songbo, Al-Enizi Abdullah M, Nafady Ayman, Tang Zhiyong, Ma Shengqian
Department of Chemistry, University of North Texas, 1508 W Mulberry St, Denton, TX 76201, USA.
School of Physical Science and Technology, Lanzhou University, No. 222 South Tianshui Road, Lanzhou, 730000, Gansu Province, P.R. China.
Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202213399. doi: 10.1002/anie.202213399. Epub 2022 Dec 7.
Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms of activation by non-metal sites of heterogeneous catalysts. Herein, as demonstrated by combined computational and experimental studies, we present a general strategy for integrating rationally designed molecular chiral frustrated Lewis pair (CFLP) with porous metal-organic framework (MOF) to construct the catalyst CFLP@MOF that can efficiently promote the asymmetric hydrogenation in a heterogeneous manner, which for the first time extends the concept of chiral frustrated Lewis pair from homogeneous system to heterogeneous catalysis. Significantly, the developed CFLP@MOF, inherits the merits of both homogeneous and heterogeneous catalysts, with high activity/enantio-selectivity and excellent recyclability/regenerability. Our work not only advances CFLP@MOF as a new platform for heterogeneous asymmetric hydrogenation, but also opens a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.
不对称氢化作为合成手性分子的开创性策略,在多相催化剂的非金属位点活化方面仍存在很大不足。在此,通过计算和实验相结合的研究表明,我们提出了一种将合理设计的分子手性受阻路易斯对(CFLP)与多孔金属有机框架(MOF)相结合的通用策略,以构建能够以多相方式有效促进不对称氢化的催化剂CFLP@MOF,这首次将手性受阻路易斯对的概念从均相体系扩展到多相催化。值得注意的是,所开发的CFLP@MOF兼具均相和多相催化剂的优点,具有高活性/对映选择性以及出色的可回收性/可再生性。我们的工作不仅推动了CFLP@MOF成为多相不对称氢化的新平台,也为不对称催化的先进催化剂的设计和制备开辟了新途径。