A stable acyl cobalt-based catalyst with exceptionally elevated activity for the carbonylation of epoxides intoβ-lactones  

酰基钴基催化剂用于高活性高稳定性环氧化物羰基化制备β-内酯

作　　者：Jianwei Jiang Vinothkumar Ganesan Inrack Choi Jeongcheol Shin Sungho Yoon Kiyoung Park 姜建伟;Vinothkumar Ganesan;崔仁洛;申庭澈;尹城镐;朴纪映(中央大学化学系,首尔,韩国;德成女子大学化学系,首尔,韩国;韩国科学技术院化学系,大田,韩国)

机构地区：[1]Department of Chemistry,Chung-Ang University,Dongjak-gu,Seoul 06974,Republic of Korea [2]Department of Chemistry,Duksung Women's University,Dobong-gu,Seoul 01369,Republic of Korea [3]Department of Chemistry,Korea Advanced Institute of Science and Technology,Yuseong-gu,Daejeon 34141,Republic of Korea

出　　处：《Chinese Journal of Catalysis》2025年第1期336-344,共9页催化学报(英文)

摘　　要：Polyhydroxyalkanoate(PHA),a well-known biodegradable polymer,featuresβ-lactones as its monomers,which can be selectively synthesized through ring-expansion carbonylation of epoxides using well-defined[Lewis acid]^(+)[Co(CO)_(4)]^(-)catalysts.However,the decomposition of[Co(CO)_(4)]^(-)species at temperatures exceeding 80℃presents a hurdle for the development of commercially viable processes under high-temperature reaction conditions to reduce reaction time.Drawing insights from stable{(acyl)Co(CO)n}intermediates involved in historical HCo(CO)_(4)-catalyzed hydroformylation processes,we sought to the high-temperature catalytic activity of epoxide ring-expansion carbonylation.The developed catalyst system,[(acetyl)Co(CO)_(2)dppp]and[(TPP)CrCl],exhibited exceptional catalytic performance with an unprecedented initial turnover frequency of 4700 h^(-1)at 100℃and a turnover numbers of 93000.Notably,the catalyst displayed outstanding stability,operating at 80℃for 168 h while selectively generatingβ-lactones.聚羟基烷酸酯(PHA)是一种被广泛应用的可生物降解聚合物,其单体为β-内酯,可以通过使用结构明确的[Lewis酸]^(+)[Co(CO)_(4)]^(-)催化剂对环氧化物进行扩环羰基化选择性合成.然而,当温度高于80℃时,[Co(CO)_(4)]物种易分解,因而制约了在高温反应条件下商业可行的工艺的发展.HCo(CO)_(4)催化的氢甲酰化过程中涉及稳定的((acyl)Co(CO)_(n))中间体,因此我们致力于提升高温条件下催化剂催化环氧化开环羰基化活性。本文制备的[(acetyl)Co(CO)dp]和[(TPP)CrCl]催化剂体系表现出较好的催化性能,100C时初始转化频率达到4700h^(-1),转化数为93000.而且该催化剂还表现出较好的稳定性,在80℃运行168h,仍能选择性地产生β-内酯.

关 键 词：Epoxide carbonylation β-Lactone Cobalttetracarbonyl Acyl cobalt carbonyl High-temperature catalytic activity 

分 类 号：O64[理学—物理化学]