Ligand effect on regioselectivity in the addition reaction of tetrachloromethane with trifluoroethene catalyzed by copper(I) complexes
The regioselectivity of the addition reaction of tetrachloromethane with trifluoroethene is influenced by the structure of the amine ligand in the copper(I) complex used as the catalyst.The regio isomer ratio varied over the range 0.86 - 2.72 indicating a significant ligand effect on the regioselectivity.The results confirm the assumption that the addition reaction proceeds in the coordination sphere of the copper complex.
19F nuclear magnetic resonance studies of halogenated propanes
The relationship between 19F chemical shifts in halogenated propanes and their structures are elucidated using MNDO calculations to determine the population of rotamers.The pairs of atom gauche to a fluorine atom and van der Waals interaction between the two terminal substituents are responsible for the 19F chemical shifts.The differences among chemical shifts in diastereomers are also discussed in terms of the conformation of molecule.
Tanuma, T.,Ohnishi, K.,Okamoto, H.,Miyajima, T.,Morikawa, S.
p. 259 - 284
(2007/10/02)
Addition of tetrachloromethane to trifluoroethene catalyzed by copper complexes
The addition of tetrachloromethane to trifluoroethene catalyzed by copper complexes gives 1:1 adducts in up to 97percent yield under mild reaction conditions.The catalytic activity and the regioselectivity of copper, ruthenium and palladium complexes and dibenzoyl peroxide have been compared.Differeneces in regioselectivity indicate that the copper-coordinated trichloromethyl radical is involved in copper-assisted addition reactions, whilst free-radical species in an uncomplexed form play a role in other cases.