Sept 2014 - Article in Chem. Comm. Published

James' paper about the development of 2-aryl-4-DMAP-N-oxides as catalysts for selective phosphorylation of alcohols is published.

James I. Murray, Rudiger Woscholski and Alan C. Spivey, 'Highly efficient and selective phosphorylation of amino acid derivatives and polyols catalysed by 2-aryl-4-(dimethylamino)pyridine-N-oxides – towards kinase-like reactivity', Chem. Comm. 2014, ASAP. DOI: 10.1039/C4CC05388E

The chemoselective phosphorylation of hydroxyl containing amino acid derivatives and polyols by phosphoryl chlorides catalyzed by 2-aryl-4-(dimethylamino)pyridine-N-oxides is described. Excellent yields and high levels of selectivity for primary (over secondary and phenolic) and for phenolic (over primary and secondary) alcohols can be achieved particularly for catalysts containing an electron deficient 2-aryl group [e.g. 2,4-bis(trifluoromethyl)phenyl]-substituted]. The low-basicity of these catalysts obviates problems of elimination in cases where this side-reaction usually compromises yields (e.g Ser → dehydro-Ala). Tyr kinase-like site-selective phosphorylation of the phenolic OH group in a Tyr, Ser and Thr-containing heptapeptide is demonstrated.