© 2016 Wiley-VCH Verlag GmbH & Co. KGaA. The reaction between benzoic acid and methylphenylacetylene to form an isocoumarin is catalyzed by Cp∗Rh(OAc)2 in the presence of Cu(OAc)2(H2O) as an oxidant and a leading example of oxidative-coupling reactions. Its mechanism was elucidated by DFT calculations with the B97D functional. The conventional mechanism, with separate reductive-elimination and reoxidation steps, was found to yield a naphthalene derivative as the major product by CO2 extrusion, contradicting experimental observations. The experimental result was reproduced by an alternative mechanism with a lower barrier: In this case, the copper acetate oxidant plays a key role in the reductive-elimination step, which takes place through a transition state containing both rhodium and copper centers. This cooperative reductive-elimination step would not be accessible with a generic oxidant, which, again, is in agreement with available experimental data.
- C-C coupling
- density functional calculations
- oxidative coupling
- reaction mechanisms
- reductive elimination