Despite the commercial desirability of catalytic carbonylation of heterocycles, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO)4–-incorporated Cr-MIL-101 (Cr-MIL-101 = Cr3O(BDC)3F, H2BDC = 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 post-synthetically introduced Co(CO)4– and the site-isolated Lewis acidic Cr(III) centers of the metal−organic framework (MOF). The heterogeneous nature of the catalyst allows the first demonstration of continuous-flow carbonylation of epoxides, attesting to the potential applicability of the heterogeneous heterocycle carbonylation strategy.

Catalytic carbonylation of heterocycles by Co(CO)4–-incorporated Cr-MIL-101

255th National Meeting (2018)

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