Abstract

The synthesis of phosphorus molecules presenting a chiral center on the P‐atom, also known as P‐stereogenic compounds, has long attracted the curiosity of the scientific community. Indeed, these chemical compounds feature many peculiar properties, allowing their use in various fields of applications, ranging from medicine to enantioselective catalysis. However, their synthesis, and more particularly the introduction and retention of the chiral information on the phosphorus center, remains a very challenging task. That is why this review article focuses on the recent advances in the enantioselective synthesis of P‐stereogenic molecules, with a particular focus on the introduction of the chiral center on the phosphorus atom. This article summarizes the main synthetic approaches directed towards the enantioselective synthesis of such chemical entities with a historical perspective. Thus, approaches based on the use of chiral auxiliaries attached to the phosphorus atom and the use of chiral stoichiometric reagents will be discussed first, as they were historically the first to be developed. Then, the recent discoveries in the catalytic and enantioselective synthesis and the direct optical resolution of P‐chiral compounds will be discussed.

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