Phosphafluorenyl lithiums:direct synthesis from white phosphorus,structure and diversified synthons

作     者：Jingyuan Hu Zhengqi Chai Wei Liu Zhe Huang Junnian Wei Wen-Xiong Zhang Jingyuan Hu;Zhengqi Chai;Wei Liu;Zhe Huang;Junnian Wei;Wen-Xiong Zhang

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)State Key Laboratory of Rare Earth Materials Chemistry and Applications&Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of EducationCollege of ChemistryPeking UniversityBeijing 100871China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第2期

页      面：322-327页

核心收录：

学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(22131001,21725201,21890721) the High-performance Computing Platform of Peking University。 

主　　题：white phosphorus organophosphorus compounds P–C bond formation P_(4)functionalization phosphafluorenyl lithium 

摘      要：While rich chemistry of phospholyl anions is discovered,phosphafluorenyl anions are only proposed as the critical intermediates for the synthesis of phosphafluorenes.In this article,we reported the direct synthesis of phosphafluorenyl lithiums from white phosphorus(P_(4))through direct P-C bond formation.The reaction between P4 and biphenyl dilithio reagents efficiently afforded phosphafluorenyl lithiums,which were further used to synthesize different kinds of organophosphorus compounds.The aggregation states of phosphafluorenyl lithiums were investigated for the first time.Mechanistic studies by DFT calculations revealed a cooperative nucleophilic attack of two C−Li bonds on P_(4)molecule.