Direct Synthesis of Phospholyl Lithium from White Phosphorus

The selective construction of P−C bonds directly from P4 and nucleophiles is an ideal and step‐economical approach to utilizing elemental P4 for the straightforward synthesis of organophosphorus compounds. In this work, a highly efficient one‐pot reaction between P4 and 1,4‐dilithio‐1,3‐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 P4 activation. Instead, a cooperative nucleophilic attack of two Csp2 Li bonds on P4, leading to simultaneous cleavage of two P−P bonds, is favorable. This mechanistic information offers a new view on the mechanism of P4 activation, as well as a reasonable explanation for the excellent yields and selectivity. This method could prove to be a useful route to P4 activation and the subsequent production of organophosphorus compounds. Pull it together: Phospholyl lithium derivatives were synthesized directly from P4 and 1,4‐dilithio‐1,3‐butadienes with excellent efficiency. DFT calculations indicate that the mechanism of this reaction differs from the well‐known stepwise cleavage of P−P bonds in P4 activation. Instead, a cooperative nucleophilic attack of two Csp2−Li bonds on P4 is preferred.