Recent advances in stoichiometric phosphine-mediated organic synthetic reactions

Organic synthetic reactions mediated by tertiary phosphines have attracted much attention in the organic chemistry community in the past two decades. These reactions can be divided into two categories: phosphine-catalyzed and stoichiometric phosphine-mediated transformations. While the phosphine-catalyzed reactions mechanistically rely on the unique properties of tertiary phosphines such as excellent nucleophilicity and good leaving group ability, the stoichiometric transformations are usually driven by nucleophilicity and strong oxyphilicity of tertiary phosphines. Since tertiary phosphines represent an important class of versatile chemical reagents in organic synthesis, stoichiometric phosphine-mediated reactions have recently demonstrated their uniqueness and high efficiency in organic synthesis, particularly with respect to the construction of carbon–carbon and carbon–heteroatom bonds, and therefore have stimulated much research interest. In this review, recent advances in stoichiometric phosphine-mediated reactions primarily including olefinations and annulations are summarized.