56112-35-7Relevant articles and documents
β-DIKETONES CONTAINING PERFLUOROISOPROPYL AND PERFLUORO-tert-BUTYL GROUPS
Knunyants, I. L.,Igumnov, S. M.
, p. 192 - 194 (1982)
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Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents
Andrella, Nicholas O.,Liu, Karen,Gabidullin, Bulat,Vasiliu, Monica,Dixon, David A.,Baker, R. Tom
, p. 422 - 432 (2018/02/17)
New coinage-metal heptafluoroisopropyl (LnM-hfip) complexes are synthesized from the metal fluoride and inexpensive hexafluoropropene (M = Ag, Cu; L = PPh3, 2,2,6,6-tetramethylpiperidine (Htmp)). Reaction of the silver Htmp complex with a Ni dibromide complex led to efficient hfip transfer to afford L2NiBr(hfip) (L = 2-ethylpyridine). Treatment of the Ni-hfip complex with ZnPh2 gave the corresponding L2NiPh(hfip) complexes, which were investigated for reductive elimination of PhCF(CF3)2. Although the desired reductive elimination proved unsuccessful, addition of carbon monoxide to L2NiPh(hfip) effected an efficient heptafluoroisopropyl carbonylative cross-coupling. Further, while the silver complex does not undergo hfip transfer to organic electrophiles, the copper complex (phen)(PPh3)Cu(hfip) (3b) effectively transfers the hfip unit to various substrates. We investigated the scope of 3b with acid chlorides toward the synthesis of perfluoroisopropyl aryl ketones. Additionally, reaction conditions for hfip transfer to p-fluorobenzyl bromide and p-fluorobenzaldehyde were identified. As a bonus, 3b was easily generated on a gram scale using commercially available copper hydride by taking advantage of a rapid hydrodefluorination to generate Cu-F in situ. Aspects of the observed reactivity are supported by DFT calculations.
A simple procedure for nucleophilic perfluoroalkylation of organic and inorganic substrates
Petrov, Viacheslav A.
, p. 3267 - 3269 (2007/10/03)
The mixture RfI and tetrakis(dimethylamino)ethylene is used for the nucleophilic perfluoroalkylation. The reaction of chlorotrimethylsilane and RfI/tetrakis(dimethylamino)ethylene in diglyme results in the formation of RfSi(CH3)3 isolated in 55-81% yield. The interaction of this system with organic electrophiles such as benzoyl and benzensulphonyl chlorides, aliphatic and aromatic aldehydes and activated ketones leads to the formation of the corresponding condensation products in 24-62% yield.