Fixation of CO 2 into Cyclic Carbonates by Halogen‐Bonding Catalysis

作者：Rui Yan, Kai Chen, Zhenjiang Li, Yuanyuan Qu, Luoyu Gao, Haoying Tong, Yongqiang Li, Jie Li, Yongzhu Hu, Kai Guo · 发表于：ChemSusChem · 年份：2020 · DOI：10.1002/cssc.202002525 · 被引用次数：72 · 研究领域：Carbon dioxide utilization in catalysis、Chemical Synthesis and Reactions、CO2 Reduction Techniques and Catalysts

Abstract Halogen bonding, parallel to hydrogen bonding, was introduced into the catalytic cycloaddition of carbon dioxide into epoxide (CCE) reactions. A series of halogen‐bond donor (XBD) catalysts of N ‐iodopyridinium halide featured with N−I bond were synthesized and evaluated in CCE reactions. The optimal XBD catalyst, 4‐(dimethylamino)‐ N ‐iodopyridinium bromide ([DMAPI]Br), under screened conditions at 100 °C, ambient pressure, and 1 mol % catalyst loading, realized 93 % conversion of styrene oxide into cyclic carbonate in 6 h. The substrate scope was successfully extended with excellent yields (mostly ≥93 %) and quantitative selectivity (more than 99 %). 1 H NMR spectroscopy of the catalyst [DMAPI]Br on substrate epoxide certified that the N−I bond directly coordinated with the epoxide oxygen. A plausible mechanism of halogen‐bonding catalysis was proposed, in which the DMAPI cation functioned as halogen‐bond donor to activate the epoxide, and the counter anion bromide attacked the methylene carbon to initiate the ring‐opening of the epoxide. CCE reactions promoted by N ‐iodopyridinium halide, exemplify a first case of halogen‐bonding catalysis in epoxide activation and CO 2 transformation.