Direct Synthesis of Phospholyl Lithium from White Phosphorus

The selective construction of P-C bonds directly from P-4 and nucleophiles is an ideal and step-economical approach to utilizing elemental P-4 for the straightforward synthesis of organophosphorus compounds. In this work, a highly efficient one-pot reaction between P-4 and 1,4-dilithio1,3-butadienes was realized, which quantitatively affords phospholyl lithium derivatives. DFT calculations indicate that the mechanism is significantly different from that of the well-known stepwise cleavage of P-P bond in P-4 activation. Instead, a cooperative nucleophilic attack of two C-sp2 Li bonds on P-4, leading to simultaneous cleavage of two P-P bonds, is favorable. This mechanistic information offers a new view on the mechanism of P-4 activation, as well as a reasonable explanation for the excellent yields and selectivity. This method could prove to be a useful route to P-4 activation and the subsequent production of organophosphorus compounds.