(606f) Ring-Expansion Carbonylation of Heterocycles By Bimetallic Ion-Pair Catalysis in Co(CO)4–-Incorporated Cr-MIL-101

Despite the commercial desirability of catalytic carbonylation of heterocycles, reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of Co(CO)₄^–-incorporated Cr-MIL-101 (Cr-MIL-101⊂Co(CO)₄, Cr-MIL-101 = Cr₃O(BDC)₃F, H₂BDC = 1,4-benzenedicarboxylic acid) as the first 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 heterobimetallic cooperativity between the postsynthetically introduced Co(CO)₄^– and the site-isolated Lewis acidic Cr(III) centers of the metal−organic framework (MOF). The heterogeneous nature of Cr-MIL-101⊂Co(CO)₄ allows continuous-flow operation of a packed-bed reactor process for a facile production and recovery of carbonylated heterocycles, highlighting the unique processing advantages conferred by the heterogeneous carbonylation pathway.

References

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2. Park, H. D.; Dincă, M.^*; Román-Leshkov, Y^*. In preparation.
3. Román-Leshkov, Y; Dincă, M; Park, H. D. Compositions and Methods for Selective Carbonylation of Heterocyclic Compounds. U.S. Application: 62/403,938. International Application: PCT/US2017/055035. Publication Number: WO 2018/067636.