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The introduction of carbonyl functionality using carbonylation in its various forms represents some of the largest volume and most successful applications of homogeneous catalysis in the chemical industry. These reactions have a diversity of mechanisms which, once understood, allow the manipulation of the catalytic processes in unique ways and offers options for interesting reactor designs. This review will focus on the generation of acetates and propionates, two of the simplest entities that can be generated by carbonylation, and discuss how mechanistic knowledge can be used to develop new catalysts and new reactor configurations in carbonylation processes when desired. Examples will include the development of (i) a Rh–MeI–Li catalyzed carbonylation of methyl acetate to acetic anhydride, (ii) a Mo catalyzed carbonylation of ethylene to propionic acid and propionic anhydride, (iii) a molecular Ir–La catalyst supported on carbon for heterogeneous carbonylation of methanol, (iv) alternative reactor designs ... |
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