Interaction of difluoromethylene phosphobetaine with heteroatom-centered electrophiles

• Published in: Journal of fluorine chemistry Vol. 220; pp. 78 - 82
• Main Authors: Trifonov, Alexey L., Panferova, Liubov I., Levin, Vitalij V., Volodin, Alexander D., Korlyukov, Alexander A., Dilman, Alexander D.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.04.2019; Elsevier; Elsevier BV
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Crystal structure; Decarboxylation; Halogen bonding; Halogenation; Iodides; Organic chemistry; Phosphobetaine; Phosphonium salts; Phosphorus; Phosphorus ylide; Physical Sciences; Quantum chemistry; Reagents; Salts; Science & Technology; X-ray diffraction; Phosphorus ylide; Halogen bonding; Phosphonium salts; Halogenation; Phosphobetaine; DIFLUOROCARBENE; ALPHA-SILYLDIFLUOROMETHYLPHOSPHONATES; TERMINAL ALKYNES; ALDEHYDES; DIFLUOROALKYLATION; ALKENES; ARYL BORONIC ACIDS; PHOSPHONATES; NUCLEOPHILIC DIFLUOROMETHYLATION; TRIFLUOROMETHYLATION
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2019.02.008

Synthesis of difluorinated phosphonium salts by interaction of the phosphobetaine reagent with halogen and chalcogen electrophiles is described. [Display omitted] •Reactions of difluoromethylene phosphobetaine.•Halogenation of fluorinated ylides.•Synthesis of fluorinated phosphonium salts. A series of difluorinated phosphonium salts were obtained by reaction of difluoromethylene phosphobetaine with halogenating reagents, as well as arylsulfenyl and arylselenyl chlorides. The reaction proceeds via decarboxylation of the phosphobetaine followed by trapping of the difluorinated phosphorus ylide by heteroatom-centered electrophiles. The crystal structures of the phosphonium salts were studied by X-ray diffraction analysis. For the salt containing the CF2I group and iodide counterion, the I⋯I interaction was identified in the solid state. The nature of this halogen bond was evaluated by quantum chemical calculations.