Through the combination of synthetic studies, NMR spectroscopy, and mass spectrometry, a new theory for the structure of the active transmetallating species in the Negishi reaction has emerged. Through careful titration and solvent studies, the effect that salt additives, such as LiBr, has on the Schlenk equilibrium has been studied in detail. The precise role of polar solvent on this equilibrium is also presented and how the solvent facilitates the formation of the critical higher-order transmetallating zincate, which we suggest is critical for the reaction to proceed. This higher order zincate now has been successfully prepared and subjected to the Negishi reaction with surprising results.

New insights into the Negishi cross-coupling reaction: The role of salt additives

243rd National Meeting (2012)

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