NMR spectroscopy studies of electronic effects and equilibrium in the organogold-to-boron transmetalation reaction and studies towards its application to the alkoxyboration addition of boron-oxygen σ bonds to alkynes.

Electronic effects in the transmetalation of an aryl group from gold to boron were investigated by NMR spectroscopy. The transmetalation reaction is more facile for increasingly electrophilic boron reagents and is in equilibrium under certain conditions. Observed tetracoordinate boronate compounds suggest a two-step, associative transmetalation reaction mechanism in which the organogold complex first delivers a nucleophilic phenyl group to the empty p orbital of boron. For certain substrates, this tetracoordinate intermediate decomposes to the tricordinate, final transmetallation product, and in others this tricordinate species remains in equilibrium with a tetracoordinate anionic boron compound. Experimental and theoretical investigations into the extension of this transmetalation reaction from a mechanistic step in our previously reported intramolecular gold-catalyzed addition of boron-oxygen σ bonds across alkynes to an intermolecular variant are discussed.2014 Elsevier Ltd. All rights reserved.