膦酰二氟甲基和膦酰硫代二氟甲基自由基。生成及其对烯烃和炔烃的加成反应。

Phosphonodifluoromethyl and phosphonothiodifluoromethyl radicals. Generation and addition onto alkenes and alkynes.

作者信息

Pignard Sébastien, Lopin Chrystel, Gouhier Géraldine, Piettre Serge R

机构信息

Laboratoire des Fonctions Azotées et Oxygénées Complexes, UMR CNRS 6014, IRCOF-Université de Rouen, Rue Tesnières, F-76821 Mont Saint Aignan, France.

出版信息

J Org Chem. 2006 Jan 6;71(1):31-7. doi: 10.1021/jo051511c.

DOI:10.1021/jo051511c

PMID:16388614

Abstract

[reaction: see text] Selanylated difluoromethylphosphonates and difluoromethylphosphonothioates are good precursors to phosphonodifluoromethyl and phosphonothiodifluoromethyl radicals, respectively. When generated in the presence of alkenes and a hydrogen donor, the corresponding alpha,alpha-difluorinated alkylphosphonates or alkylphosphonothioates are produced in fair to good yields. The use of alkynes results in the formation of alpha,alpha-difluorinated allyl derivatives in useful yields. The presence of the sulfur atom in phosphonothiodifluoromethyl radicals usually translates into higher isolated yields.

摘要

[反应：见正文] 硒代二氟甲基膦酸酯和二氟甲基硫代膦酸酯分别是二氟甲基膦基和硫代二氟甲基膦基自由基的良好前体。当在烯烃和氢供体存在下生成时，相应的α,α-二氟代烷基膦酸酯或烷基硫代膦酸酯以中等至良好的产率生成。使用炔烃会以有用的产率形成α,α-二氟代烯丙基衍生物。硫代二氟甲基膦基自由基中硫原子的存在通常会转化为更高的分离产率。