Tandem Catalytic Acrylonitrile Cross-Metathesis and Hydrogenation of Nitriles with Ruthenium Catalysts: Direct Access to Linear α,ω-Aminoesters from Renewables

Organométalliques: Matérieux et Catalyse, Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes, Campus de Beaulieu, 35042 Rennes, France.
ChemSusChem (Impact Factor: 7.66). 08/2012; 5(8):1410-4. DOI: 10.1002/cssc.201200086
Source: PubMed


Fraternité, Solidarité & complémentarité en Catalyse: Tandem alkene cross-metathesis of acrylonitrile with long-chain alkene and hydrogenation catalysis is performed by using a single ruthenium-alkylidene catalyst precursor. The protocol allows the catalytic transformation of unsaturated fatty acids, derivatives of plant oils, into α,ω-aminoesters. A key step involves the reduction of nitrile-ester intermediates into aminoesters, the precursors of polyamides, with alkene metathesis catalyst residue under mild conditions.

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    • "Among renewables, fatty acid methyl esters (FAMEs) arising from plant oils have recently received attention for the production of polymer precursors obtained by efficient and selective cross‐metathesis transformations [4] [5]. In particular, cross‐metathesis reactions with ethylene [6] [7] [8] [9] [10] [11], methyl acrylate [12] [13] and acrylonitrile[14] [15] [16] [17] have been extensively studied for the synthesis of polyolefin, polyester, and polyamide precursors, respectively. Acrolein is another important acrylic reagent of high potential as the formyl group provides a direct access to a broad range of organic functionalities. "
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    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 post-transformations of the formyl group availableThe ruthenium-catalyzed cross-metathesis of fatty acid methyl esters with acrolein is presented. The bifunctional formyl-esters are valuable precursors for subsequent transformations such as the tandem cross-metathesis/hydrogenation reaction delivering a hydroxyl-ester in one step.
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    Advanced Synthesis & Catalysis 10/2012; 354(14‐15). DOI:10.1002/adsc.201200385 · 5.66 Impact Factor
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    ABSTRACT: The modification of methyl ricinoleate by etherification of the hydroxyl group was accomplished by using a nonclassical ruthenium-catalyzed allylation reaction and also by esterification. Methyl ricinoleate derivatives were engaged in ring-closing metathesis (RCM) reactions leading to biosourced 3,6-dihydropyran and α,β-unsaturated lactone derivatives with concomitant production of polymer precursors. Sequential RCM/hydrogenation and RCM/cross-metathesis were also implemented as a straightforward method for the synthesis of tetrahydropyran and lactone derivatives as well as valuable monomers (i.e., polyamide precursors).
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