Recent Breakthroughs in P₄ Chemistry: Towards Practical, Direct Transformations into P₁ Compounds

Abstract

For several decades, academic researchers have been intensively studying the chemistry of white phosphorus (P 4 ) in the hope of developing direct methods for its transformation into useful P-containing products. This would bypass the hazardous, multistep procedures currently relied on by industry. However, while academically interesting P 4 activation reactions have become well established, their elaboration into useful, general synthetic procedures has remained out of reach. Very recently, however, a series of independent reports has begun to change this state of affairs. Each shows how relatively simple and practical synthetic methods can be used to access academically or industrially relevant P 1 compounds from P 4 directly, in "one pot" or even in a catalytic fashion. These reports mark a step change in the field of P 4 chemistry, and suggest its possible transition from an area of largely academic interest to one with the promise of true synthetic relevance.

Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

“…The convenient construction of organophosphorus compounds (OPCs) based on white phosphorus (P 4 ) activation will be one of the important ways to solve the synthetic problem. 239,240 In summary, the Ph-BPE ligand is increasingly used due to its high efficiency in a wide range of asymmetric reactions, but the potential of Ph-BPE -based asymmetric chemistry is far from being fully recognized.…”

Ternary Photoredox/Nickel/Halide Catalysis for the Phosphorylation of Alcohols with White Phosphorus

“…Dialkyl phosphites (DAPIs), (RO) 2 P­(O)­H, are essential building blocks in the production of various industrial products, such as plastic flame retardants, metal extractants, and fine chemical products like pesticides and pharmaceutical intermediates (Scheme a). , Due to its remarkable importance in the field of organophosphorus synthesis, developing a new strategy to replace traditional PCl 3 -based methods is crucial due to the hazardous and corrosive nature of PCl 3 , which is produced by the chlorination of white phosphorus (P 4 ) with dangerous and toxic molecular chlorine (Scheme b). − Chemists have been studying the direct transformation of P 4 into useful P 1 -containing products for several decades. − Despite significant academic interest in P 4 activation by metal complexes, , C­(sp 2 )–Li reagents, , and electrochemistry, the direct conversion of white phosphorus to industrially useful organic phosphorus compounds remains a significant challenge. − …”