Highly Efficient Conversion of Both Propargylic Alcohols and Propargylic Amines with CO2 Activated by Noble-Metal-Free Catalyst Cu2O@ZIF-8.

作者：Bin Zhao, Ai-Ling Gu, Zhi-Lei Wu, Yaxin Zhang, Huiling Cui, Tian-ding Hu · 发表于：Angewandte Chemie · 年份：2022 · DOI：10.1002/anie.202114817 · 被引用次数：95 · 研究领域：Medicine

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.