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

Abstract

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.