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Fixation of CO 2 into Cyclic Carbonates by Halogen‐Bonding Catalysis
Author(s) -
Yan Rui,
Chen Kai,
Li Zhenjiang,
Qu Yuanyuan,
Gao Luoyu,
Tong Haoying,
Li Yongqiang,
Li Jie,
Hu Yongzhu,
Guo Kai
Publication year - 2021
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.202002525
Subject(s) - epoxide , chemistry , catalysis , halogen bond , iodide , bromide , halogen , cycloaddition , hydrogen bond , photochemistry , polymer chemistry , inorganic chemistry , organic chemistry , molecule , alkyl
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.