Functionalization of P₄ through Direct P−C Bond Formation

Abstract

Research on chlorine‐free conversions of P4 into organophosphorus compounds (OPCs) has a long track record, but methods that allow desirable, direct P−C bond formations have only recently emerged. These include the use of metal organyls, carbenes, carboradicals, and photochemical approaches. The versatile product scope enables the preparation of both industrially relevant organophosphorus compounds, as well as a broad range of intriguing new compound classes. Herein we provide a concise overview of recent breakthroughs and outline the acquired fundamental insights to aid future developments.

Phosphorus recovery and recycling – closing the loop

“…A large range of phosphoruscontaining products have been synthesised from P 4 ; this topic has been reviewed extensively, with reviews focusing on P 4 activation by transition metals, main-group systems and via electrocatalytic functionalization, and will not be further discussed here. 23 White phosphorus is the most reactive allotrope of phosphorus, so efforts to use more benign red phosphorus as an alternative to PCl 3 necessitate more forcing conditions. Red phosphorus, which is formed by heating white phosphorus to 250 1C, has a chain-like polymeric structure, and is used as-is in matchboxes and flameretardants, but is not relevant as a separate raw material for follow-up chemistry.…”

Reversible Activation and Transfer of White Phosphorus by Silyl‐Stannylene

“…Organophosphorus compounds offer unique structural and electronic properties and therefore have gained considerable attention in the past decades [1] . Their synthesis classically involves the energy intensive and hazardous chlorination of white phosphorus (P 4 ) [1d,e] . As an alternative, the activation of P 4 under mild conditions and subsequent transformation to organic molecules presents an attractive approach towards P 4 utilization [1a–c,e,f] .…”

A Systematic Survey of the Reactivity of Chlorinated N2P2, NP3 and P4 Ring Systems

“…In particular,o ur grouph as al ong-standing interest in cyclic oligophosphanesa nd aminophosphanes.S uch ring systems show ad iverse reactionb ehaviour and have therefore attracted the interest of many researchersd uring the past few decades. [9][10][11][12][13][14][15] Among these classes of compounds, especially fourmembered N 2 P 2 ring systems were thoroughlys tudied, as detailed in an umber of review articles. [16][17][18][19][20] Outoft he many possible substitution patterns at the N 2 P 2 ring system, those species with halogen substituents (e.g.…”