Generation of boryl-nitroxide radicals from a boraalkene the nitroso ene reaction.

Examples of isolated boron substituted nitroxide radicals are rare. The reaction of the reactive cyclic boraalkene 3 with nitrosobenzene yields a mixture of the [2 + 2] cycloaddition product 4a, the -nitroxide radicals 5a and 6a and the azoxybenzene co-product 7a a bora nitroso ene reaction pathway, the boron analogue of the nitroso ene reaction. The products were separated by flash chromatography, and the -nitroxide radicals were characterized by X-ray diffraction and EPR spectroscopy. Radical 5a was shown to be a hydrogen atom abstractor. Both the -nitroxide radicals are more easily oxidized compared to TEMPO, as shown by cyclic voltammetry.