Phosphonodifluoromethyl and phosphonothiodifluoromethyl radicals. Generation and addition onto alkenes and alkynes.
[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.
Pignard
Sébastien
S
Laboratoire des Fonctions Azotées et Oxygénées Complexes, UMR CNRS 6014, IRCOF-Université de Rouen, Rue Tesnières, F-76821 Mont Saint Aignan, France.
Lopin
Chrystel
C
Gouhier
Géraldine
G
Piettre
Serge R
SR
D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005609:Free Radicals / Q000138:chemical synthesis / Q000737:chemistry; D008745:Methylation; D015394:Molecular Structure; D010758:Phosphorus / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D000475:Alkenes; D000480:Alkynes; D005609:Free Radicals; D013438:Sulfhydryl Compounds; D010758:Phosphorus; D005461:Fluorine