An Industrially Viable Catalyst System for Palladium‐Catalyzed Telomerizations of 1,3‐Butadiene with Alcohols
- 12 August 2004
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 10 (16), 3891-3900
- https://doi.org/10.1002/chem.200400182
Abstract
The telomerization reaction of 1,3-butadiene with alcohols to give alkyl octadienyl ethers in the presence of palladium–carbene catalysts has been studied in detail. Unprecedented catalyst efficiency with turnover numbers (TON) up to 1 500 000 and turnover frequencies (TOF) up to 100 000 h−1 have been obtained after optimization for the reaction of methanol in the presence of an excess of in situ generated carbene ligands. High yields (75–97 %) and catalyst productivities (TON 15 000–100 000) are observed for other aliphatic alcohols and phenols. For comparison five carbene–palladium(0) complexes have been synthesized and characterized by X-ray crystallography. Both electronic and steric effects on the stability and reactivity of the catalysts have been discussed on the basis of density functional theory calculations.Keywords
This publication has 66 references indexed in Scilit:
- Telomerization of Amines Mediated by Cationic N-Heterocyclic Carbene (NHC) Palladium ComplexesOrganometallics, 2003
- Competition between Carbene and Pseudo η3-Allyl Bonding Modes in a Palladium(II) Complex of a Functionalized Bis(imidazolium) LigandOrganometallics, 2001
- 1,6-Diene Complexes of Palladium(0) and Platinum(0): Highly Reactive Sources for the Naked Metals and [L−M0] FragmentsJournal of the American Chemical Society, 1999
- Telomerization of butadiene with methanol catalysed by cationic palladium complexes containing a bidentate phosphinoamino ligandJournal of Molecular Catalysis A: Chemical, 1999
- Thermally Stable Mesomorphic Palladium(II)−Carbene ComplexesChemistry of Materials, 1999
- Selective synthesis of octadienyl and butenyl ethers via reaction of 1,3-butadiene with alcohols catalyzed by homogeneous palladium complexesJournal of Molecular Catalysis A: Chemical, 1998
- Reactivity and syn-anti isomerization of (.eta.3-geranyl)- and (.eta.3-neryl)palladium complexes. Evidence for electronic control of the regiochemistry of nucleophilic additionOrganometallics, 1985
- η3‐Allylpalladium‐VerbindungenAngewandte Chemie, 1985
- Higher Telomers in the Pd-Catalyzed Reaction of Butadiene with AlcoholsAngewandte Chemie International Edition in English, 1982
- Höhere Telomere bei der Pd‐katalysierten Reaktion von Butadien mit AlkoholenAngewandte Chemie, 1982