Synthesis and Characterization of Alkoxy Spirophosphoranes Prepared from Hydrospirophosphoranes and Sodium Alcoholates

The Atherton–Todd-type reaction of hydrospirophosphoranes (HSPs) and sodium alcoholates was investigated. Direct alkoxylation of HSPs was accomplished with sodium alcoholates in acetonitrile under nitrogen atmosphere. The stereochemistry mechanism of the alkoxidation of HSPs was proposed by the 31 P NMR tracing experiment. The reaction proceeded via the chlorinated spirophosphorane intermediate with stereoretention of the configuration at phosphorus, followed by the rear and front attack of alkoxide anions to produce alkoxy spirophosphoranes. The reaction mechanism well explained the results of the reaction of HSPs with sodium alcoholates.