Computational Prediction and Experimental Confirmation of the Reaction between 1-Lithio-1,3-butadiene and White Phosphorus Affording Phospholyl Lithium
Yaqi Zhao, Zhengqi Chai, Zhiyi Song, Junnian Wei, and Wen-Xiong Zhang*
Organometallics 2025, 44, 300-306.
https://doi.org/10.1021/acs.organomet.4c00451
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, DFT 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 C-Li bond towards P4 and P-P bonds towards 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.
