Hydrophosphorylation of C=O/N Bonds Using Organophosphine Oxides or Sulfides

Abstract

Abstractα‐Functionalized phosphorus compounds are an important class of biologically relevant molecules. The synthesis of these compounds often proceeds through the hydrophosphorylation of a C=E bond, with the most well‐known transformation being the Kabachnik‐Fields reaction. The nature of the phosphorus reagent is an important aspect of the hydrophosphorylation reaction. The Kabachnik‐Fields reaction uses H‐phosphonates (RO)2P(O)H, and similarities are often applied to 2° phosphine chalcogenides (R2P(Ch)H). However, the reactivities of the P−C and P−OR molecules differ quite dramatically, which changes the operative mechanism as well as subsequent downstream chemistry. We provide an in‐depth analysis of hydrophosphorylation of C=E (E=O, N) bonds with organophosphine chalcogenides. Additional discussion and a critical appraisal are provided on the similarities and differences between the H‐phosphonate and phosphine chalcogenide chemistry.