Computational Prediction and Experimental Confirmation of the Reaction between 1‑Lithio-1,3-Butadiene and White Phosphorus Affording Phospholyl Lithium

The direct construction of C–P bonds from white phosphorus (P4) and nucleophilic reagents is of great scientific importance and application value. In this work, density functional theory calculations reveal the reaction mechanism of P4 with the mono-lithium reagent, namely, 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene. The construction of C–P bonds is realized through the sequential nucleophilic attacks of the C–Li bond toward P4 and P–P bonds toward the butadiene skeleton. The calculation results were confirmed by the model reaction of 1,2,3,4-tetraethyl-1-lithiobuta-1,3-diene with P4 providing the corresponding phospholyl lithium selectively. This work combining computational prediction with experimental confirmation opens a new avenue for the discovery of the selective reaction between mono-lithium reagents and white phosphorus.