Gu Ai-Ling, Zhang Ya-Xin, Wu Zhi-Lei, Cui Hui-Ya, Hu Tian-Ding, Zhao Bin
Department of Chemistry, Key Laboratory of Advanced Energy Material Chemistry, MOE, Renewable Energy Conversion and Storage Center (RECAST), Nankai University, Tianjin, 300071, China.
College of Chemistry and Environmental Science, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Hebei University, Baoding, 071002, China.
Angew Chem Int Ed Engl. 2022 May 2;61(19):e202114817. doi: 10.1002/anie.202114817. Epub 2022 Feb 3.
The cyclization reactions of propargylic alcohols and propargylic amines with CO are important in industrial applications, but it was a great challenge that non-noble-metal catalysts catalyzed both reactions under mild conditions. Herein, the catalyst Cu O@ZIF-8 was prepared by encapsulating Cu O nanoparticles into robust ZIF-8, and it can effectively catalyze the cyclization of both propargylic alcohols and propargylic amines with CO into valuable α-alkylidene cyclic carbonates and oxazolidinones with turnover numbers (TONs) of 12.1 and 19.6, which can be recycled at least five times. The mechanisms were further uncovered by NMR, FTIR, C isotope-labeling experiments and DFT calculations, in which Cu O and DBU can synergistically activate the C≡C bond and the hydroxy/amino group of substrates. Importantly, it is the first example of a noble-metal-free catalyst that can catalyze both propargylic alcohols and propargylic amines with CO simultaneously.
炔丙醇和炔丙胺与一氧化碳的环化反应在工业应用中很重要，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。在此，通过将氧化铜纳米颗粒封装到坚固的ZIF-8中制备了催化剂Cu O@ZIF-8，它可以有效地催化炔丙醇和炔丙胺与一氧化碳环化生成有价值的α-亚烷基环状碳酸酯和恶唑烷酮，周转数（TONs）分别为12.1和19.6，并且可以至少循环使用五次。通过核磁共振（NMR）、傅里叶变换红外光谱（FTIR）、碳同位素标记实验和密度泛函理论（DFT）计算进一步揭示了反应机理，其中氧化铜和1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）可以协同活化底物的碳碳三键以及羟基/氨基。重要的是，这是无贵金属催化剂同时催化炔丙醇和炔丙胺与一氧化碳反应的首个实例。
