Selective and Controllable Defluorophosphination andDefluorophosphorylation of Trifluoromethylated Enones: AnAuxiliary Function of the Carbonyl Group

Li-Wen Sun,^aYa-Fei Hu,^aWen-Jun Ji,^aPeng-Yuan Zhang,^aMengtao Ma,^bZhi-Liang Shen^*aand Xue-Qiang Chu^*a

^aTechnical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China. E-mails: ias_zlshen@njtech.edu.cn; xueqiangchu@njtech.edu.cn.

^bDepartment of Chemistry and Materials Science, College of Science, Nanjing Forestry University, Nanjing 210037, China.

Abstract:The auxiliary function of a carbonyl group in thetunable defluorophosphination and defluorophosphorylation oftrifluoromethylated enones with P(O)-containing compounds wasdemonstrated. Controlled replacement of one or two fluorineatoms in trifluoromethylated enones while maintaining highchemo- and stereoselectivity was achieved under mild conditions,thus enabling diversity-oriented synthesis of skeletally diverseorganophosphorus libraries (Z)-difluoro-1,3-dien-1-yl phosphi-nates, (1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl phosphi-nates, and (E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-onesingood yields with excellent functional group tolerance.

OrganicLetters2023,25, 3745-3749. (Impact factor: 5.2)

论文链接：https://doi.org/10.1021/acs.orglett.3c01215