Details

Autor(en) / Beteiligte

• Sicard, Alexandre J.
• Ghaffari, Behnaz
• Gabidullin, Bulat M.
• Ovens, Jeffrey S.
• Hughes, Russell P.
• Baker, R. Tom

Titel

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH2CF2): Selective β‑F vs β‑H Elimination

Ist Teil von

• Journal of the American Chemical Society, 2022-12, Vol.144 (49), p.22713-22721

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2022

Link zum Volltext

Quelle

MEDLINE

Beschreibungen/Notizen

• Hydrofluoroolefins (HFOs) constitute the newest generation of fluorocarbon refrigerants and foam-blowing agents due to their reduced global warming potential vs their saturated analogues. To identify new synthetic routes to HFOs, we show that reactions of bulky Ni(0) phosphine and −NHC complexes with vinylidene difluoride (VF2) afford μ-fluoro-1,1,3-trifluorobut-3-enyl Ni complexes. Moreover, addition of triisopropylsilane allows for reductive elimination of the reduced product2,4,4-trifluoro-1-butenedemonstrating the Ni-catalyzed hydrodefluorodimerization of VF2. Accompanying DFT calculations identify the T-shaped nickelacyclopentane intermediate that spontaneously undergoes selective intramolecular β-F (vs β-H) elimination.