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An Industrially Viable Catalyst System for Palladium‐Catalyzed Telomerizations of 1,3‐Butadiene with Alcohols
Author(s) -
Jackstell Ralf,
Harkal Surendra,
Jiao Haijun,
Spannenberg Anke,
Borgmann Cornelia,
Röttger Dirk,
Nierlich Franz,
Elliot Mark,
Niven Stuart,
Cavell Kingsley,
Navarro Oscar,
Viciu Mihai S.,
Nolan Steven P.,
Beller Matthias
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400182
Subject(s) - catalysis , telomerization , carbene , palladium , chemistry , steric effects , reactivity (psychology) , organic chemistry , methanol , turnover number , phenols , medicinal chemistry , photochemistry , medicine , alternative medicine , pathology
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.