Palladium- or nickel-catalyzed reactions of alkenylmetals with unsaturated organic halides as a selective route to arylated alkenes and conjugated dienes: scope, limitations, and mechanism

Journal Article · Wed Apr 15 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00242a024· OSTI ID:6802604

Negishi, E; Takahashi, T; Baba, S; Van Horn, D E; Okukado, N

Stereo- and regiodefined alkenylmetals containing Al, Zr, and Zn react with aryl and alkenyl iodides and bromides in the presence of catalytic amounts of Pd or Ni complexes containing phosphine ligands, such as PPh/sub 3/, to give the corresponding cross-coupled products. Palladium catalysts permit nearly 100% stereospecificity in both alkenyl-aryl and alkenyl-alkenyl coupling reactions, whereas nickel catalysts lead to partial stereochemical scrambling in the alkenyl-alkenyl coupling. Although many other metals including Li, Mg, Cd, Hg, B, Si, Sn, Ti, and Ce were also used, the results were inferior to those obtained with Al, Zr, and Zn under the conditions used in the present study. The turnover numbers for the palladium-catalyzed reactions of PhI with (E)-1-octenylmetals containing Al, Zr, and Zn were 2, 3, and > 2000 mmol of (E)-1-octenylbenzene (8) per mmol of Pd(PPh/sub 3/)/sub 4/ per hour at room temperature, respectively. The stoichiometric reaction of PhPd(PPh/sub 3/)/sub 2/I (6) with 1.2 equiv of (E)-1-octenylzinc chloride (7) in a 2:1 mixture of CD/sub 2/Cl/sub 2/ and THF was examined in detail. The reaction follows second-order kinetics (k/sub 2/ = 2.9 L/(mol.min) at 0/sup 0/C) to give 8 without the buildup of any intermediate.

• Research Organization: Purdue Univ., West Lafayette, IN
• OSTI ID: 6802604
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:8; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
ALUMINIUM COMPOUNDS
BORON COMPOUNDS
BROMIDES
BROMINE COMPOUNDS
CADMIUM COMPOUNDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CERIUM COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
KINETICS
LIGANDS
LITHIUM COMPOUNDS
MAGNESIUM COMPOUNDS
MERCURY COMPOUNDS
METALS
NICKEL
NUMERICAL DATA
ORGANIC COMPOUNDS
PALLADIUM
PHOSPHINES
PHOSPHORUS COMPOUNDS
PLATINUM METALS
RARE EARTH COMPOUNDS
REACTION KINETICS
SILICON COMPOUNDS
STEREOCHEMISTRY
STOICHIOMETRY
TIN COMPOUNDS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
ZINC COMPOUNDS
ZIRCONIUM COMPOUNDS