Oxidation of a P-C Bond under Mild Conditions
Date of Issue2015
School of Physical and Mathematical Sciences
The reactivity of phosphenium dication [(Ph3P)2C-P-NiPr2]2+, 12+, towards pyridine N-oxide (O-py) has been investigated. The resulting oxophosphonium dication [(Ph3P)2C(NiPr2)P(O)(O-py)]2+, 22+, was surprisingly stabilized by a less nucleophilic O-py ligand instead of pyridine (py). This compound was then identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P[BOND]C bond through a mechanism usually observed for Baeyer–Villiger oxidations. This oxygen insertion appears to be the first example of a Baeyer–Villiger oxidation involving O-py.
Chemistry - A European Journal
© 2015 Wiley-VCH Verlag. This is the author created version of a work that has been peer reviewed and accepted for publication by Chemistry - A European Journal, Wiley-VCH Verlag. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1002/chem.201503922].