Organophosphorus chemistry based on elemental phosphorus: advances and horizons

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.