Palladium Catalysed Acid‐Free Carboxytelomerisation of 1,3‐Butadiene with Alcohols Accessing Pelargonic Acid Derivatives Including Triglycerides under Selectivity Control

Abstract

Palladium catalysed carboxytelomerisation of 1,3-butadiene with alcohols yields unsaturated C 9 -pelargonic esters in an atom-economic and straightforward way. Although carboxytelomerisation is of current interest, limitations of applicable alcohol substrates have not been fully investigated. In here, we present the transfer of the catalytic system comprising palladium acetate and tri-n-butyl phosphine in pyridine to a broad variety of 20 alcohols with vast difference in nucleophilicity and sterical demands yielding the corresponding esters in a 100% atom economic manner. Effects of nucleophilicity and sterical demands were revealed for monoalcohols, di-and polyols. Whilst yields, chemoselectivity and E/Z-selectivity of the pelargonic acid derivatives were excellent with up to 99%, selectivity towards mono-, di-and triesters could be controlled successfully. Finally, the reaction profile of the carboxytelomerisation glycerol was uncovered, yielding up to 97% of industrially relevant unsaturated C 9 -short chain fats.

Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

“…Besides, the commercial d t bpx was also effective in promoting such a transformation but partially lost time efficiency . By contrast, the combination of palladium salts and monodentate phosphine ligands was widely employed in the carboxytelomerization of conjugated dienes with a specific ratio of dienes to alcohols. − …”

Palladium-catalyzed synthesis of mixed anhydridesviacarbonylative telomerization

“…Additionally, they were able to control the degree of esterification via control over the 1,3-butadiene concentration. 12 These di- and triesters can be used as synthetic fats, lubricants or polymer precursors.…”