13846-40-7Relevant academic research and scientific papers
An industrially viable catalyst system for palladium-catalyzed telomerizations of 1,3-butadiene with alcohols
Jackstell, Ralf,Harkal, Surendra,Jiao, Haijun,Spannenberg, Anke,Borgmann, Cornelia,Roettger, Dirk,Nierlich, Franz,Elliot, Mark,Niven, Stuart,Cavell, Kingsley,Navarro, Oscar,Viciu, Mihai S.,Nolan, Steven P.,Beller, Matthias
, p. 3891 - 3900 (2004)
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 1500000 and turnover frequencies (TOF) up to 100000h-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 15000-100000) are observed for other aliphatic alcohols and phenols. For comparison five carbenepalladium(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.
Development of a 4,4′-biphenyl/phosphine-based COF for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene
Hausoul, Peter J. C.,Eggenhuisen, Tamara M.,Nand, Deepak,Baldus, Marc,Weckhuysen, Bert M.,Klein Gebbink, Robertus J. M.,Bruijnincx, Pieter C. A.
, p. 2571 - 2579 (2013/09/24)
The improved synthesis, characterisation and application of a microporous 4,4′-biphenyl/phosphine-based covalent organic framework (COF) for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene with phenol and glycerol are presented. The solid polyphosphine is amorphous, microporous and an excellent support for Pd(acac)2. Solid-state NMR and DRIFT analysis of materials of varying Pd-loading show that bis-phosphine complexes of palladium are preferably formed. Under solvent- and base-free conditions, high conversions and selectivities are obtained for this catalyst material with both phenol and glycerol as substrates. The product selectivity, with both butenylation and telomerisation activity observed with phenol, can be tuned by variation of the metal loading. For glycerol it is shown that the selectivity to the undesired tri telomer is low under all applied conditions and, remarkably, that the heterogeneous catalyst outperforms its homogeneous PPh 3-based counterpart.
A highly efficient catalyst for the telomerization of 1,3-dienes with alcohols: First synthesis of a monocarbenepalladium(0)-olefin complex
Jackstell, Ralf,Andreu, Mario Gomez,Frisch, Anja,Selvakumar, Kumaravel,Zapf, Alexander,Klein, Holger,Spannenberg, Anke,Roettger, Dirk,Briel, Oliver,Karch, Ralf,Beller, Matthias
, p. 986 - 989 (2007/10/03)
Industrial reaction improved: The first monocarbenepalladium(0)-olefin complex has been isolated and characterized (see structure; Pd orange, N green, S yellow, O blue). The complex exhibited unprecedented high catalyst productivity and selectivity for in
