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
Leibniz-Institut für Organische Katalyse an der Universität Rostock e.V., Buchbinderstrasse 5-6, 18055 Rostock, Germany.
Chemistry. 2004 Aug 20;10(16):3891-900. doi: 10.1002/chem.200400182.
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.
详细研究了在钯-卡宾催化剂存在下，1,3-丁二烯与醇发生的调聚反应，生成烷基辛二烯基醚。在甲醇与过量原位生成的卡宾配体反应的条件下进行优化后，获得了前所未有的催化剂效率，周转数（TON）高达1500000，周转频率（TOF）高达100000 h⁻¹。对于其他脂肪醇和酚，观察到高产率（75 - 97%）和催化剂生产率（TON 15000 - 100000）。为作比较，合成了五种卡宾-钯(0)配合物，并通过X射线晶体学进行了表征。基于密度泛函理论计算，讨论了电子效应和空间效应对催化剂稳定性和反应活性的影响。
