title: Synthesis of 1,4-dichloro-1,3-butadienes by rhodium complex catalyzed reaction of terminal alkynes with trichloroacetyl chloride.
abstract: Chlorinative dimerization of terminal alkynes with trichloroacetyl chloride as chlorine donor proceeds in the presence of rhodium catalysts to give (Z,Z)-1,4-dichloro-1,3-butadienes stereoselectively. Ligand screening has revealed that reactions using sterically bulky and electron-donating ligands like trimesitylphosphine are high yielding. The reaction is compatible with a range of functional groups to give the title compounds nearly quantitatively in most cases. A mechanistic possibility involving coupling of beta-chloroalken-1-yl intermediate has been discussed.
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
authors.forename: Taigo
authors.initials: T
authors.lastname: Kashiwabara
authors.forename: Kouichirou
authors.initials: K
authors.lastname: Fuse
authors.forename: Takeshi
authors.initials: T
authors.lastname: Muramatsu
authors.forename: Masato
authors.initials: M
authors.lastname: Tanaka
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002070:Butadienes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry; D062845:Chloroacetates; D019281:Dimerization; D006843:Hydrocarbons, Chlorinated / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D008956:Models, Chemical; D010720:Phosphines / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D014238:Trichloroacetic Acid / Q000737:chemistry
chemical_list: D000480:Alkynes; D002070:Butadienes; D002712:Chlorides; D062845:Chloroacetates; D006843:Hydrocarbons, Chlorinated; D008024:Ligands; D010720:Phosphines; D014238:Trichloroacetic Acid; C037540:trichloroacetyl chloride; D012238:Rhodium; C044646:phosphine