Computational\nPrediction and Experimental Confirmation\nof the Reaction between 1‑Lithio-1,3-Butadiene and White Phosphorus\nAffording Phospholyl Lithium

The direct construction of C–P bonds from white\nphosphorus\n(P<sub>4</sub>) and nucleophilic reagents is of great scientific importance\nand application value. In this work, density functional theory calculations\nreveal the reaction mechanism of P<sub>4</sub> with the <i>mono</i>-lithium reagent, namely, 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene.\nThe construction of C–P bonds is realized through the sequential\nnucleophilic attacks of the C–Li bond toward P<sub>4</sub> and\nP–P bonds toward the butadiene skeleton. The calculation results\nwere confirmed by the model reaction of 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene\nwith P<sub>4</sub> providing the corresponding phospholyl lithium\nselectively. This work combining computational prediction with experimental\nconfirmation opens a new avenue for the discovery of the selective\nreaction between <i>mono</i>-lithium reagents and white\nphosphorus.