86862-27-3Relevant academic research and scientific papers
Asymmetric Radical Reaction in the Coordination Sphere. III. Asymmetric Addition of Trichloromethanesulfonyl Chloride and Carbon Tetrachloride to Olefins Catalysed by a Ruthenium(II) Complex with Chiral Ligand
Kameyama, Masayuki,Kamigata, Nobumasa
, p. 3687 - 3692 (1987)
The asymmetric addition of trichloromethanesulfonyl chloride to styrene in the presence of a catalytic amount of ruthenium(II) complex with chiral ligands, Ru2Cl43 or Ru2Cl43, proceeds under mild conditions to give optically active 1:1 adducts, 1,1,1,3-tetrachloro-3-phenylpropane (2), with the extrusion of sulfur dioxide.When (-)-DIOP or (+)-DIOP was used as a chiral ligand of the ruthenium(II) complex, (R)-(+)-(2) or (S)-(-)-(2), was obtained with about 10percent enantiomeric excess, respectively.A reaction mechanism involving a radical redox transfer mechanism was proposed; the asymmetric induction was attributed to the restricted configuration of the radical intermediates confined in the coordination sphere of the ruthenium complex with chiral ligands.
REACTIVITY OF SUBSTITUTED STYRENES IN THE CATALYTIC ADDITION REACTION WITH THE TRICHLOROMETHYL RADICAL
Hajek, Milan,Silhavy, Premysl,Spirkova, Bozena
, p. 2949 - 2955 (2007/10/02)
Relative reactivities have been investigated in the catalytic addition of tetrachloromethane to substituted styrenes by the competitive method.The polar effects of substituents on benzene ring were correlated with Hammett equation for a copper and ruthenium catalyst, giving ρ values equal to -0.39 and -0.18 respectively.The results indicate that in contrast to classical additions the catalytic addition of tetrachloromethane is not a free radical chain process but that the trichloromethyl radical, presumably coordinated, reacts with the carbon-carbon double bond via in nersphere pathways.
ADDITION OF SULFONYL CHLORIDES TO OLEFINS IN THE PRESENCE OF CATALYTIC AMOUNTS OF DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II)
Kamigata, Nobumasa,Sawada, Hideo,Suzuki, Norihiro,Kobayashi, Michio
, p. 199 - 204 (2007/10/02)
Reactions of sulfonyl chlorides with olefins catalysed by dichlorotris(triphenylphosphine)ruthenium(II) have been studied.Methanesulfonyl and arenesulfonyl chlorides added to 1-alkenes to give 1 : 1 adducts in high yields.Telomer formation is not observed, therefore the present reaction provides a general and convenient method for synthesis of β-chlorosulfones.A radical-chain mechanism is proposed for the reaction.
