Park Hoyoung D, Dincă Mircea, Román-Leshkov Yuriy
Department of Chemical Engineering and Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
ACS Cent Sci. 2017 May 24;3(5):444-448. doi: 10.1021/acscentsci.7b00075. Epub 2017 Mar 21.
Despite the commercial desirability of epoxide carbonylation to β-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO)-incorporated Cr-MIL-101 (Co(CO)⊂Cr-MIL-101, Cr-MIL-101 = CrO(BDC)F, HBDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selectivity, and substrate scope are on par with those of the reported homogeneous catalysts. We ascribe the observed performance to the unique cooperativity between the postsynthetically introduced Co(CO) and the site-isolated Lewis acidic Cr(III) centers in the metal-organic framework (MOF). The heterogeneous nature of Co(CO)⊂Cr-MIL-101 allows the first demonstration of gas-phase continuous-flow production of β-lactones from epoxides, attesting to the potential applicability of the heterogeneous epoxide carbonylation strategy.
尽管环氧化合物羰基化生成β-内酯在商业上具有吸引力，但该过程对均相催化剂的依赖使其工业应用面临挑战。在此，我们报告了一种用于环氧化合物扩环羰基化反应的、负载有Co(CO)的Cr-MIL-101（Co(CO)⊂Cr-MIL-101，Cr-MIL-101 = CrO(BDC)F，HBDC = 1,4-苯二甲酸）多相催化剂的制备及应用，其活性、选择性和底物范围与已报道的均相催化剂相当。我们将所观察到的性能归因于后合成引入的Co(CO)与金属有机框架（MOF）中位点隔离的路易斯酸性Cr(III)中心之间独特的协同作用。Co(CO)⊂Cr-MIL-101的多相性质首次实现了从环氧化合物气相连续流生产β-内酯，证明了多相环氧化合物羰基化策略的潜在适用性。
