Palladium-catalyzed reactions of butadiene

COMPARISON OF NICKEL- AND PALLADIUM-CATALYZED REACTIONS OF BUTADIENE... 

At first Smutny carried out the palladium-catalyzed reaction of butadiene with phenol using PdCl2 as a catalyst (28, 29). Phenoxybutene and o- and p-butenylphenols were obtained in low conversion and yield. When pyridine was added, 8-phenoxy-l,6-octadiene was obtained in low yield. However, 8-phenoxy-l,6-octadiene and 3-phenoxy-l,7-octadiene... 

The main path of the palladium-catalyzed reaction of butadiene is the dimerization. However, the trimerization to form /j-1, 3,6,10-dodeca-tetraene takes place with certain palladium complexes in the absence of a phosphine ligand. Medema and van Helden observed, while studying the insertion reaction of butadiene to 7r-allylpalladium chloride and acetate (32, 37), that the reaction of butadiene in benzene solution at 50°C using 7r-allylpalladium acetate as a catalyst yielded w-1,3,6,10-dodecatetraene (27) with a selectivity of 79% at a conversion of 30% based on butadiene in 22 hours. 

Various telomers and oligomers now available by the palladium-catalyzed reactions of butadiene with various nucleophiles are very useful compounds for organic synthesis, because these compounds have functional groups at one end and terminal double bonds at the other end. Several natural products have been synthesized from the telomers. 

Palladium-Catalyzed Reactions of Butadiene C. Uses of the Telomers of Malonate and Acetoacetate... 

Behr A, Juszak KD (1983) Palladium-catalyzed reaction of butadiene and carbon-dioxide. J Organomet Chem 255 263-268... 

A new synthetic method for steroids has been developed using a butadiene dimer (66) as a building block and the palladium-catalyzed oxidation as the key reaction. 3-Acetoxy-l,7-octadiene (66), prepared by the palladium-catalyzed reaction of butadiene with acetic acid, is hydrolyzed and oxidized to... 

A new synthetic method for steroids has been developed using a butadiene dimer (66) as a building block and the palladium-catalyzed oxidation as the key reaction.3-Acetoxy-l,7-octadiene (66), prepared by the palladium-catalyzed reaction of butadiene with acetic acid, is hydrolyzed and oxidized to l,7-octadien-3-one (67) in high yield. The enone (67) is a very useful reagent for bisanellation because its termiiud double bond can be regarded as a masked ketone which can be readily unmasked by the palladium catalyst to form the l,S-diketone (68) after Michael addition at the enone moiety of (67 Scheme 20). Thus, the enone (67) is the cheapest and most readily available bisanellation reagent, permitting a simple total synthesis of steroids. 

J. Tsuji, Adv. Organomet. Chem., 1979, 17, 141-193. Palladium-Catalyzed Reactions of Butadiene and Isoprene. 

The palladium catalyzed reaction of butadiene with carbon dioxide affords mixtures of the cyclic adducts 32 and 33 and linear adducts. The yield of the six-membered ring lactone increases when using a catalyst containing more basic phosphine ligands (PCys, P-i-Prs). ... 

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