title: Double-Bond Isomerization: Highly Reactive Nickel Catalyst Applied in the Synthesis of the Pheromone (9Z,12Z)-Tetradeca-9,12-dienyl Acetate.
abstract: A highly reactive nickel catalyst comprising NiCl2(dppp) or NiCl2(dppe) with zinc powder, ZnI2 and Ph2PH, was applied in the isomerization of terminal alkenes to Z-2-alkenes. The double-bond geometry of the 2-alkene can be controlled via the reaction temperature to yield the 2-Z-alkenes in excellent yields and high Z-selectivities. The formation of other constitutional isomers, such as 3-alkenes, is suppressed on the basis of the proposed mechanism via a 1,2-hydride shift from the metal to the Ph2P ligand. The nickel-catalyzed isomerization reaction was then applied in the synthesis of (9Z,12Z)-tetradeca-9,12-dienyl acetate, a pheromone with a 2Z,5Z-diene subunit.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Felicia
authors.initials: F
authors.lastname: Weber
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Anastasia
authors.initials: A
authors.lastname: Schmidt
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Philipp
authors.initials: P
authors.lastname: Röse
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Michel
authors.initials: M
authors.lastname: Fischer
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Olaf
authors.initials: O
authors.lastname: Burghaus
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35043 Marburg, Germany.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Hilt