Capture of Electron-Deficient Species with Aryl Halides. New Syntheses of Hypervalent Iodonium Ylides

Article abstract of DOI:10.1021/ja00291a044

We have demonstrated the aryl iodide capture of β-diketocarbenes, generated from the diazo compound by using rhodium(II) acetate, under very mild conditions.This is a useful general preparative method for iodonium ylides under non-hydroxylic conditions.The termal, catalytic, and photochemical decompositions of various azides in the presence of aryl iodides were carried out.With highly reactive nitrenes, intramolecular rearrangement takes precedence over capture.In the case of p-tuloenesulfonyl azide, thermolysis in the presence of aryl iodides requires conditions under which the iminoiodane is itself decomposed.The capture of oxene by iodobenzene is discussed.The application of these capture processes is discussed as a synthetic route to hypervalent ylides as well as on the basis of mechanism.