Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH2═CF2): Selective β-F vs β-H Elimination
Alexandre J Sicard1, Behnaz Ghaffari1, Bulat M Gabidullin2
1Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
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.
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