Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH<sub>2</sub>═CF<sub>2</sub>): Selective β-F <i>vs</i> β-H Elimination
Alexandre J. Sicard, Behnaz Ghaffari, Bulat Gabidullin, Jeffrey S. Ovens, Russell P. Hughes, R. Tom Baker
Abstract
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.