Journal of the American Chemical Society, Vol.140, No.34, 10669-10672, 2018
Continuous-Flow Production of Succinic Anhydrides via Catalytic beta-Lactone Carbonylation by Co(CO)(4)subset of Cr-MIL-101
Industrial synthesis of succinic acid relies on hydrocarbon oxidation or biomass fermentation routes that suffer from energy-costly separation processes. Here we demonstrate an alternate route to succinic anhydrides via beta-lactone carbonylation by heterogeneous bimetallic ion-pair catalysis in Co(CO)(4)(-)-incorporated Cr-MIL-101 (Co(CO)(4)subset of Cr-MIL-101, Cr-MIL-101 = Cr3O(BDC)(3)F, H2BDC = 1,4-benzenedicarboxylic acid). Postsynthetically introduced Co(CO)(4)(-) facilitates CO insertion to beta-lactone substrates activated by the Lewis acidic Cr(III) centers of the metal-organic framework (MOF), leading to catalytic carbonylation with activity and selectivity profiles that compare favorably to those reported for homogeneous ion-pair catalysts. Moreover, the heterogeneous nature of the MOF catalyst enables continuous production of succinic anhydride through a packed bed reactor, with room temperature beta-propiolactone carbonylation activity of 1300 mol(Anhydride).mol(Co)(-1) over 6 h on stream. Simple evaporation of the fully converted product stream yields the desired anhydride as isolated solids, highlighting the unique processing advantages conferred by this first example of heterogeneous beta-lactone carbonylation pathway.