Gas-phase synthesis of phenyl oxoborane (C6H5BO) via the reaction of boron monoxide with benzene

J Org Chem. 2013 Dec 6;78(23):11896-900. doi: 10.1021/jo401942z. Epub 2013 Nov 19.


Organyl oxoboranes (RBO) are valuable reagents in organic synthesis due to their role in Suzuki coupling reactions. However, organyl oxoboranes (RBO) are only found in trimeric forms (RBO3) commonly known as boronic acids or boroxins; obtaining their monomers has proved a complex endeavor. Here, we demonstrate an oligomerization-free formation of organyl oxoborane (RBO) monomers in the gas phase by a radical substitution reaction under single-collision conditions in the gas phase. Using the cross molecular beams technique, phenyl oxoborane (C6H5BO) is formed through the reaction of boronyl radicals (BO) with benzene (C6H6). The reaction is indirect, initially forming a van der Waals complex that isomerizes below the energy of the reactants and eventually forming phenyl oxoborane by hydrogen emission in an overall exoergic radical-hydrogen atom exchange mechanism.