Gets there in the end: The large rate difference of the slow reductive elimination and the fast transmetalationretrotransmetalation steps allows Pd to visit complexes 3, 2, and 1 many times before coupling from 2 takes place. This fast recurrence of transformations offers many opportunities for the formation of undesired homocoupling products in Negishi reactions by statistically accessible "mistaken" retrotransmetalation events in the multitude of processes preceding the slower irreversible reductive elimination of the coupling product. (Figure Presented) © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
|Journal||Chemistry - A European Journal|
|Publication status||Published - 2 Aug 2010|
- C-C coupling
- Density functional calculations
- Homogeneous catalysis
- Negishi coupling
Fuentes, B., García-Melchor, M., Lledós, A., Maseras, F., Casares, J. A., Ujaque, G., & Espinet, P. (2010). Palladium round trip in the Negishi coupling of trans- [PdMeCl(PMePh <inf>2</inf>)<inf>2</inf>] with ZnMeCl: An experimental and DFT study of the transmetalation step. Chemistry - A European Journal, 16(29), 8596-8599. https://doi.org/10.1002/chem.201001332