The palladium-catalysed reaction of butadiene with acetic acid in the presence of phosphites

Total Synthesis of Leukotrienes from Butadiene

“…We found that the dimerization of butadiene with acetic acid in the presence of Pd(acac) 2 (0.2%), tri-o-tolyl phosphite (0.2%) and NaOAc (3%) can be accomplished at room temperature producing a mixture of the octadienol acetates 9 (13%), 10 (76%) and 11 (11%) (the ratio of isomers was determined by 1 H NMR spectroscopy) in 90% yield after distillation (Scheme 2). [35] The ratio of isomers is similar to the results reported by Keim et al using a bimetallic palladium catalyst in CH 3 CN at 60°C. [37] Cleavage of the acetate with a catalytic amount of K 2 CO 3 in methanol at room temperature gives the octadienols 12, 13 and 14 in 95% yield after distillation (Scheme 2).…”

“…[33] A few publications describe the dimerization of butadiene at 85Ϫ90°C in water or acetic acid in the presence of a palladium catalyst, a triphenylphosphane derivative and triethylamine. [34] Triphenylphosphane can be replaced by tri-o-tolyl phosphite to give higher yields, [35] although neither of these articles mentions the presence of 2-cis-octadienol acetate which accounts for more than 10% of the products formed. Longer reaction times have been reported to increase the amount of the 3-acetoxy isomer in the mixture of octadienol acetates.…”

Telomerization: Advances and Applications of a Versatile Reaction

“…[90] The telomerization of butadiene with acetic acid [Eq. (5)] yields acetoxyoctadiene, which can be used as starting compound for the synthesis of various natural and flavoring materials.…”

Telomerisation – Fortschritte und Anwendungen einer vielseitigen Reaktion

“…Obwohl Carbonsäuren, besonders Essigsäure, bekannte Nucleophile sind, wurden die jeweiligen Telomerisationen seit den grundlegenden Arbeiten von Walker et al [89] sowie Rose und Lepper [90] [92] Darüber hinaus wurde kürzlich die Telomerisation von Butadien mit Essigsäure als Gas-flüssig-Reaktion unter Verwendung von Pd/PPh 3 als Katalysatorsystem durchgeführt. [93] Bei halbkontinuierlichen Versuchen ist Essigsäure nur unter Verwendung eines Lösungsmittels wie 1,4-Dioxan aktiv.…”