Journal of the American Chemical Society 2006-04-12

[3,3]-rearrangements of phosphonium ylides.

Marcelle L Ferguson, Todd D Senecal, Todd M Groendyke, Anna K Mapp

Index: J. Am. Chem. Soc. 128(14) , 4576-4577, (2006)

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Abstract

Allylic phosphonium ylides are readily generated by the combination of an allylic alcohol, a carbene, and a chlorophosphite. Here we demonstrate that these intermediates undergo a thermal [3,3]-rearrangement to provide single isomers of homoallylic phosphonates in good to excellent yields. This new reaction manifold for phosphorus ylides is tolerant of a range of substitution patterns on the reactants and provides access to structurally complex intermediates for the synthesis of enzyme inhibitors, aminophosphonic acids, and natural products.