Palladium-Catalyzed Telomerization Of Butadiene Research Articles

Efficient Telomerization of Butadiene with Starch in Water: The Role of the Surfactant

The synthesis of hydrophobic starch was performed via palladium-catalyzed telomerization of butadiene with native starch. This reaction is efficiently performed in water in the presence of neutral or cationic surfactant with high HLB. After optimization of the reaction conditions, TOF up to 446 was achieved.

Neutral pentosides surfactants issued from the butadiene telomerization with pentoses: preparation and amphiphilic properties

Interfacial properties of octadienyl pentosides prepared by the palladium-catalyzed telomerization of butadiene with free pentoses have been evaluated and compared to those of mixtures issued from the autoclaving process.

Synthesis of C 8 alkyl glycosides via palladium-catalyzed telomerization of butadiene with O-benzylated aldoses

Conditions of the butadiene telomerization with benzylated aldoses with a free anomeric hydroxyl, which efficiently furnish the corresponding octadienyl compounds have been determined. Deprotection and hydrogenation of the telomers over Pd/C led to the octyl glycosides.

Palladium-catalyzed telomerization of butadiene with ethylene glycol in liquid single phase and biphasic systems: control of selectivity and catalyst recycling

Abstract The palladium-catalyzed telomerization of 1,3-butadiene (Bu) with ethylene gylcol (EG) has been studied in liquid single phase and aqueous biphasic systems. All important parameters have been examined, including temperature, catalyst system, catalyst concentration, Bu/EG ratio, P/Pd ratio, solvent and reaction time. In homogeneous phase mixtures of 2-(2,7-octadienyloxy)ethanol ( 1a ) and 2-(1-ethenyl-5-hexenyloxy)ethanol ( 1b ) were formed in yields up to 60%, but also ditelomers ( 2 ) and butadiene dimers ( 3 ) were produced in significant amounts. In aqueous biphasic systems, however, using a palladium catalyst with the triphenylphosphinetrisulfonate (TPPTS) ligand, the monotelomers 1a and 1b were obtained in 80% yield with more than 95% selectivity. A mechanism is proposed explaining the observed differences in selectivity. The aqueous catalyst phase could be recycled six times resulting only in a slight decrease of activity. The products 1a and 1b were hydrogenated in quantitative yield to the corresponding saturated compounds 2-octyloxyethanol ( 6a ) and 2-(1-ethyl-hexyloxy)ethanol ( 6b ) using a Pd/Al 2 O 3 catalyst under mild conditions. The products can be used for a variety of applications like plasticizers, cosmetics and solvents.

Palladium-Catalyzed Telomerization of Butadiene with Starch

In order to modify the hydrophilic properties of native starch for its incorporation in polymers, the telomerization of butadiene with native starch was investigated. Low to moderate degrees of substitution (DS=0.04–0.52) were obtained depending upon experimental conditions, particularly, reaction time, temperature and solvent. With 0.3‰ water-soluble palladium catalyst (Pd/TPPTS), the reaction occurred in i-PrOH/NaOH 0.1 N solvent mixture even at 50 °C and after 3 h reaction the DS reached 0.08, a value suitable for the application.

Palladium-Catalyzed Reactions for the Synthesis of Fine Chemicals, 16 – Highly Efficient Palladium-Catalyzed Telomerization of Butadiene with Methanol

Palladium-Catalyzed Reactions for the Synthesis of Fine Chemicals, 16 – Highly Efficient Palladium-Catalyzed Telomerization of Butadiene with Methanol

Control of Chemo- and Regioselectivity in the Palladium-Catalyzed Telomerization of Butadiene with Methanol − Catalysis and Mechanism

The palladium-catalyzed telomerization reaction of butadiene with methanol has been examined with the aim of controlling the chemoselectivity (telomerization vs. dimerization products) and regioselectivity (linear vs. branched telomerization product) of the reaction. We have shown that the reaction temperature, ligand-to-metal ratio and ratio of substrates exert a large influence on the selectivity of the reaction. Selectivities of up to 97% for the desired linear telomerization product 1 can be achieved below 50 °C by employing both low PPh3/Pd and butadiene/methanol ratios. Mono(phosphane)palladium(0)−diallyl ether complexes, Ar3P−Pd[(CH2=CHCH2)2O] (5), serve as new catalysts for the reaction. In order to gain a mechanistic understanding of the observed selectivity effects, we synthesized the phosphane(octadienyl)palladium(II) complexes 7a and 9a as model compounds for key reaction intermediates and examined their stoichiometric reactions with the methoxide nucleophile. Based on our results, we propose an extension of the known telomerization mechanism that accounts for the observed selectivity effects.

Palladium-catalyzed telomerization of butadiene with ammonia

The telomerization reaction of butadiene with ammonia catalyzed by palladium—phosphine complexes has been studied. Tri(2,7-octadienyl)amine and di(2,7-octadienyl)(1-vinyl-5-hexenyl)amine were obtained as major products. The reaction proceeds smoothly in organic solvents containing water. The presence of certain amounts of water is essential. The branched di(2,7-octadienyl)(1-vinyl-5-hexenyl)amine could be rearranged to the linear tri(2,7-octadienyl)amine by the palladium catalyst.

パラジウム触媒で得られるブタジエンテロマーを利用した天然化合物の新しい合成法

Butadiene telomers, easily prepared by the palladium-catalyzed telomerization of butadiene with various nucleophiles are extremely useful starting materials for natural product syntheses. The following natural products were synthesized in short steps by using several butadiene telomers : Steroid (19-nortestosterone), macrolides (diplodialides, 9-decanolides, lasiodiplodin, zearalenone, recifeiolide, curvularin), Matsutake alcohol, lipoic acid, pellitorin, dihydrojasmone, methyl dihydrojasmonate, muscone, civetone, pyrethrolone, 12-acetoxy-1, 3-dodecadiene, royal jelly acids and queen substance. In these syntheses, Wacker type oxidation of terminal double bonds to methyl ketones catalyzed by PdCl2-CuCl is used in key steps.