The Wittig Reaction

In 1953 Wittig and Geissler found that reaction of benzophenone with methylenetriphenylphosphorane gave 1,1-diphenylethylene and triphenylphosphine oxide in almost quantitative yield; the phosphine had been prepared from triphenylmethylphosphonium bromide and phenyl lithium. The discovery led to the development of a new method for the synthesis of olefins, under the name Wittig reaction. One advantage of this new method is that the carbonyl group is replaced specifically by a carbon-carbon double bond without the formation of isomeric olefins. In contrast, the older method of converting carbonyl compounds to olefins using the Grignard reaction usually give a mixture of isomeric olefins. Another advantage is the Wittig reaction is carried out under mild conditions. Discussions of modern techniques for the preparation of methylene phosphoranes are included in this review.