title: Chiral phosphine-olefin ligands in the rhodium-catalyzed asymmetric 1,4-addition reactions.
abstract: A full overview on the use of chiral phosphine-olefin ligands 1 in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds is described. Effective chiral environment of a Rh/1 complex was shown to resemble that of a Rh/(R,R)-Ph-bod* complex by comparing the experimental results as well as the X-ray crystal structures. High catalytic activity of a Rh/1 complex was disclosed and the catalytic cycle involving a trimer-monomer equilibrium was established through mechanistic studies using a reaction calorimeter and (31)P NMR spectroscopy. A negative nonlinear effect derived from an inactive trimer-active monomer equilibrium of the catalyst was also successfully observed.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan.
authors.forename: Wei-Liang
authors.initials: WL
authors.lastname: Duan
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Iwamura
authors.forename: Ryo
authors.initials: R
authors.lastname: Shintani
authors.forename: Tamio
authors.initials: T
authors.lastname: Hayashi
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D001897:Boronic Acids / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D007700:Kinetics; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry
chemical_list: D000475:Alkenes; D001897:Boronic Acids; D001643:Bridged Bicyclo Compounds; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D012238:Rhodium