Reactions of perfluoroalkylcopper compounds. Part V. The preparation of some polyfluoroalkyl-substituted acids and alcohols

Abstract

Reaction of perfluoroheptylcopper(i) with (€) -1.2-di-iodoethylene gave (E) -1 H.2H-l-iodopentadecafluoronon-1 -ene (I) which with copper(i) cyanide in dimethylformamide yielded (€) -1 H,2H-1 -cyanopentadecafluoronon-1 -ene (11). Hydrolysis of (11) with sulphuric acid under vigorous conditions afforded (€) -2H.3H-pentadecafluorodec-2-enoic acid (111) whichwas readily hydrogenated to 2H.2H.3H.3H-pentadecafluorodecanoic acid (IV). Reduction of (IV) with lithium aluminium hydride afforded I H.1 H,2H,2H,3H,3H-pentadecafluorodecanol (V). Mild hydrolysis of the nitrile (11) gave (€)-2H.3H-pentadecafluorodec-2-enamide (VI). Reaction of 1.3-diiodohexafluoropropane with copper bronze and an excess of (E) -1.2-di-iodoethylene similarly afforded (1 €,6E) -3,3,4,4,5,5-hexafluoro-l,7-di-iodohepta-l,6-diene (VII) and (1 €,

Trifluoromethylation of Alkenyl Bromides and Iodides (Including 5-Iodouracils) with (CF3)2Hgand Cu (“Trifluoromethylcopper”)1

“…Yagupolskii had reported high-temperature trifluoromethylations of aryl bromides and iodides with (CF 3 ) 2 Hg/Cu, but such reactions of CF 3 Cu with vinyl halides have not been investigated carefully. Coupling of perfluoroalkylcopper reagents with ( E )-1,2-diiodoethene gave products with retained configurations . However, vicinal rather than gem-disubstituted alkenes had been obtained by analogous treatment of 1-bromo-1-perfluoroalkylethenes .…”

“…Coupling of perfluoroalkylcopper reagents with (E)-1,2-diiodoethene gave products with retained configurations. 9 However, vicinal rather than gem-disubstituted alkenes had been obtained by analogous treatment of 1-bromo-1-perfluoroalkylethenes. 10 Coupling of other haloalkenes with CF 3 Cu has been reported, but the cyclic and symmetrical alkenes or E/Z mixtures employed did not allow definitive stereochemical analysis.…”

Highly Regioselective Cyclotrimerization of 1-Perfluoroalkylenynes Catalyzed by Nickel

“…The fluorinated enynes were prepared according to the procedures shown in Schemes −3. Thus, monosubstituted perfluoroalkylenyne 1a and disubstituted perfluoroalkylenyne 1d were prepared by the copper-mediated perfluorohexylation of ( E )-1,2-diiodoethylene 8 5 followed by the Sonogashira coupling of the product 9 with alkynes (Scheme ). Other disubstituted enynes ( 1b , c ) were prepared from the iodoperfluoroolefins 12 , which were prepared by the transition metal-catalyzed addition of 1-iodoperfluorohexane to alkynes (Scheme ) .…”

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

“…Zur Herstellung von Perfluoralkylarenen aus Arylhalogeniden [417a] und von Perfluoralkyl-substituierten Alkenen aus Alkenylhalogeniden [426] wurden zuerst nucleophile Perfluoralkylkupferreagentien eingesetzt. Durch Verwendung ionischer Flüssigkeiten als Lçsungsmittel für die Perfluoralkylierung von Arylhalogeniden konnte die Reaktionstemperatur von 150 auf 75 8C gesenkt werden.…”