Ma Hui-Chao, Zhao Chen-Chen, Chen Gong-Jun, Dong Yu-Bin
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan, 250014, P. R. China.
Nat Commun. 2019 Jul 29;10(1):3368. doi: 10.1038/s41467-019-11355-x.
For seeking high enantiopurity, the previously reported thermal asymmetric catalysis is usually carried out at low temperature sometimes with limited yield, that is, the high enantiomeric excess (ee) usually at the cost of high yield. Thus, the achieving both high stereoselectivity and yield is an enormous challenge. We report herein two metal nanoparticle (M NP)-loaded and porphyrin-containing homochiral covalent organic framework (CCOF)-based composite catalysts, and their application in the thermally-driven asymmetric one-pot Henry and A-coupling reactions. All the reactions are conducted at elevated temperatures with both excellent stereoselectivity and yield which resulted from the synergy of CCOF confinement effect and M NP catalytic activation. Notably, the needed thermal energy for the asymmetric reactions herein is derived from the photothermal conversion via porphyrin-based CCOF upon irradiation with visible light. Remarkably, the CCOF confinement effect can be effectively maintained up to 100 °C for the asymmetric one-pot Henry and A-coupling reactions herein.
为了获得高对映体纯度，先前报道的热不对称催化通常在低温下进行，有时产率有限，也就是说，高对映体过量（ee）通常是以高收率为代价的。因此，同时实现高立体选择性和高收率是一个巨大的挑战。我们在此报告了两种负载金属纳米颗粒（M NP）且含卟啉的手性共价有机框架（CCOF）基复合催化剂，以及它们在热驱动不对称一锅法亨利反应和A-偶联反应中的应用。所有反应均在高温下进行，具有优异的立体选择性和产率，这是CCOF限域效应和M NP催化活化协同作用的结果。值得注意的是，本文中不对称反应所需的热能来自于基于卟啉的CCOF在可见光照射下的光热转换。值得注意的是，对于本文中的不对称一锅法亨利反应和A-偶联反应，CCOF限域效应在高达100 °C时仍能有效保持。
