Chemistry of Cyclic Phosphorus Compounds. 3. Synthesis of Pheromones Having an γ,δ-Unsaturated Ketone System from 1,1-Diphenylphospholanium Perchlorate

Article abstract of DOI:10.1021/jo00265a006

1,1-Diphenylphospholanium perchlorate (1) was converted into the sex pheromones 5a,b of the Japanese female peach fruit moth by use of use tandem Wittig reactions.The ylide of 1 formed with potassium tert-butoxide reacted with heptanal to give Z phosphine oxide 2 with stereoselectivity.The reaction of the anion of 2 with dimethyl disulfide followed by the Horner-Wittig reaction with nonanal or octanal gave the corresponding diene derivatives 4a,b.Hydrolysis of 4a,b afforded the desired the Z γ,δ-unsaturated ketones 5a,b.On the other hand, the conversion of 9, which was derived from methylthio-substituted compound 6, gave an E and Z isomeric mixture of 5b (4:5).