Stereospecific Coupling of Alcohols and Carbanion Nucleophiles through a Circular P(V) Activation Manifold

We report a method for the stereospecific construction of sp³-sp³ carbon-carbon bonds using alcohols and carbanion nucleophiles. The process is based on a circular phosphorus(V) manifold which starts and ends with triphenylphosphine oxide. The redox neutral approach eliminates the need for hazardous diazodicarboxylate oxidants and allows for recovery and recycling of triphenylphosphine oxide. Alcohol activation is achieved <i>in situ</i> through formation of alkoxyphosphonium triflates, which are kinetically stable, and undergo coupling with exogenous carbanion nucleophiles. In this manner, a range of alcohols undergo deoxyalkylation with inversion of configuration in moderate to excellent yield.