Cross‐metathesis of fatty acid methyl esters with acrolein: An entry to a variety of bifunctional compounds

Abstract

The cross-metathesis of renewable fatty acid methyl esters with acrolein was investigated. The bifunctional formyl-esters obtained are interesting compounds for further transformations into bifunctional polymer precursors. Several experimental parameters and ruthenium catalysts have been evaluated. Best results were obtained with thermally pre-treated fatty acid methyl esters (FAMEs). The reactions performed with high efficiency with low catalyst loadings allowing TONs as high at 1000. An acetal protected acrolein was also used, enabling improvement of the reaction performances. A tandem cross-metathesis/hydrogenation reaction without isolation of the formyl intermediate delivered the expected alcohol ester in good yield. Practical applications:The cross-metathesis of FAMEs with acrolein provides access to a broad range of bifunctional compounds of interest for the manufacture of polymers, considering the multiple posttransformations of the formyl group available

Cross metathesis of bio-sourced fatty nitriles with acrylonitrile

“…Acrolein has also been used as cross metathesis partner to introduce a reactive aldehyde that can be easily transformed into a fatty alcohol or an amine derivative [22][23][24].…”

Alkene Metathesis for Transformations of Renewables

“…[87] Of note, they highlighted the dramatic influence of the feed purity. If the necessity to use low hydroperoxidecontaining methyl oleate is a known issue necessitating pre-treatment of the oil feed, [88][89][90][91][92] the influence of the ethylene gas purity was studied and found to be also a major parameter to consider for achieving high TONs.…”

Ethenolysis: A Green Catalytic Tool to Cleave Carbon–Carbon Double Bonds

“…Among them, the sequence involving several olefin metathesis transformations can be highlighted. Self‐metathesis produces diesters and cross‐metathesis with a variety electron‐deficient alkenes, such as acrylates and equivalents, acrolein, acrylonitrile, allyl chloride, allyl acetate, but‐3‐enenitrile, or pent‐4‐enenitrile, provides useful α,ω‐bifunctional polymer precursors (Scheme ). Metathesis not only with double bonds but also with triple bonds makes possible a straightforward access to long‐chain conjugated dienes that cannot be produced from internal linear olefins …”