Organophosphorus chemistry based on elemental phosphorus: advances and horizons

Abstract

The results of studies on the application of elemental phosphorus for the synthesis of important organophosphorus compounds are surveyed and summarized. Currently, this trend represents a synthetically, environmentally and technologically attractive alternative to classical organophosphorus chemistry based on toxic and corrosive phosphorus chlorides. Direct phosphination and phosphinylation of organic compounds with elemental phosphorus (discussed in the first part of the review) basically extend the range of available phosphines, phosphine chalcogenides and phosphinic acids and provides further development of their synthetic potential (discussed in the second part of the review). It is shown that the breakthrough in this area is largely due to the discovery of reactions of elemental phosphorus (white and red) with various electrophiles in superbasic suspensions and emulsions derived from alkali metal hydroxides and to the development of electrochemical, electrocatalytic and catalytic activation of white phosphorus. The bibliography includes 299 references.

Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus

“…The classical way to synthesise phosphines is via salt metathesis or hydrophosphination starting from PCl 3 or PH 3 , respectively (Fig. 1) 12,13,17 . In both cases, the targeted variation of the organic substituents is synthetically very challenging.…”

Hydrostannylation of Red Phosphorus: A Convenient Route to Monophosphines

“…Those few systems that have been reported for the direct transformation of P red typically depend on the use of harsh conditions and extremely strong reagents such as alkali metals. For example, significant contributions in this field have been provided by Trofimov and Gusarova, based on the activation of P red by “superbasic” media (aqueous KOH/DMSO) and the direct phosphorylation of electrophilic alkenes, alkynes and (het)aryl halides to afford organophosphorus compounds such as phosphines, phosphine oxides and phosphinic acids (Scheme 1b, top) [3b,9] . A different approach, initially reported by Brandsma et al [10] .…”

Organophosphorus Azoles Incorporating a Tetra-, Penta-, and Hexacoordinated Phosphorus Atom: NMR Spectroscopy and Quantum Chemistry

“…Analysis of the NMR spectra shows that compound 5 existed in the form of two isomers which were assigned by the measurement of spin-spin coupling constants 3 JРН that sharply differed between the configurational isomers with respect to the double bond [33]. In addition to these data, it was interesting to test the possibility of using 31 Р NMR chemical shifts for the configuration assignment of compounds containing a double bond С=С linked to a phosphorus atom.…”