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

被引：6

作者：

Sicard, Alexandre J. ^{[2
]}

Ghaffari, Behnaz ^{[2
]}

Gabidullin, Bulat M. ^{[2
]}

Ovens, Jeffrey S. ^{[2
]}

Hughes, Russell P. ^{[1
]}

Baker, R. Tom ^{[2
]}

机构：

[1] Dartmouth Coll, Dept Chem, Hanover, OH 03755 USA

[2] Univ Ottawa, Ctr Catalysis Res & Innovat, Dept Chem & Biomol Sci, Ottawa, ON 165 6N5, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2022年 / 144卷 / 49期

基金：

加拿大自然科学与工程研究理事会;

关键词：

FLUORINE BOND ACTIVATION; C-F; FLUOROALKYL COMPLEXES; HFC; 134A; TETRAFLUOROETHYLENE; TRIMERIZATION; ETHYLENE; FLAMMABILITY; ALDEHYDES; DYNAMICS;

D O I：

10.1021/jacs.2c10448

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 mu-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 Tshaped nickelacyclopentane intermediate that spontaneously undergoes selective intramolecular beta-F (vs beta-H) elimination.

引用

页码：22713 / 22721

页数：9

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