PR3 efficiently catalyzes the addition of H‐spirophosphorane to electron‐deficient alkenes to give the spirophosphoranes with a pentacoordinate P−C bond in moderate to excellent yields. This practical procedure was conducted by using PR3 as an organocatalyst, which avoided the use of an additional base, traditional heating, and metal reagents. The investigation of the reaction mechanism showed that the zwitterion intermediate served as the base to further catalyze hydrospirophosphorane. Then the spirophosphoranide formed as a nucleophile attacked electron‐deficient alkene to give the addition products. This reaction is a first and simple hydrophosphorylation reaction of alkenes to construct pentacoordinate P−C bond under organocatalysis
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