南开大学赵斌团队开发了无贵金属催化剂Cu2O-ZIF8激活CO2与炔丙醇和炔丙胺的高效转化。相关研究成果发表在2022年1月11日出版的《德国应用化学》。
炔丙醇和炔丙胺与CO2的环化反应在工业应用中具有重要意义,但非贵金属催化剂在温和条件下催化这两种反应是一个巨大的挑战。
该文中,研究人员通过将Cu2O纳米颗粒包埋到坚固的ZIF-8中制备了催化剂Cu2O@ZIF-8,它可以有效地催化炔丙醇和炔丙胺与CO2的环化反应,生成有价值的α-亚烷基环碳酸酯和恶唑烷酮,其周转数(吨)分别为12.1和19.6,可循环至少5次。
NMR、FTIR、13C同位素标记实验和DFT计算进一步揭示了Cu2O和DBU协同激活C≡C键和底物的羟基/氨基。重要的是,其是第一个能够同时催化炔丙醇和炔丙醇胺与CO2反应的无贵金属催化剂。
附:英文原文
Title: Highly Efficient Conversion of Both Propargylic Alcohols and Propargylic Amines with CO2 Activated by Noble-Metal-Free Catalyst Cu2O@ZIF-8
Author: Bin Zhao, Ai-Ling Gu, Zhi-Lei Wu, Ya-Xin Zhang, Hui-Ya Cui, Tian-Ding Hu
Issue&Volume: 2022-01-11
Abstract: The cyclization reactions of propargylic alcohols and propargylic amines with CO 2 are important in industrial applications, but it was great challenge that non-noble-metal catalysts catalyzed both reactions under mild conditions. Herein, the catalyst Cu 2 O@ZIF-8 was prepared by encapsulating Cu 2 O nanoparticles into robust ZIF-8, and it can effectively catalyze the cyclization of both propargylic alcohols and propargylic amines with CO 2 into valuable α-alkylidene cyclic carbonates and oxazolidinones with the turnover number (TON) of 12.1 and 19.6, which can be recycled at least five times. The mechanisms were further uncovered by NMR, FTIR, 13 C isotope labeling experiments and DFT calculations, in which Cu 2 O and DBU can synergistically activate the C≡C bond and the hydroxy/amino group of substrates. Importantly, it is the first sample that noble-metal-free catalyst can catalyze both propargylic alcohols and propargylic amines with CO 2 simultaneously.
DOI: 10.1002/anie.202114817
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202114817
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx