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Updated: Jan 9, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Stereospecific Coupling of Alcohols and Carbanion Nucleophiles through a Circular P(V) Activation Manifold
Isabel L Wood1, Stephen P Argent2, Ross M Denton1
1The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham NG7 2TU, U.K.
Abstract:
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 in situ 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.
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