Cross‐metathesis with acrylonitrile and applications to fatty acid derivatives

Abstract

International audienceIn this minireview, we report on the state of the art concerning the cross-metathesis of acrylonitrile with olefins. A special focus is given to catalytic conditions that are suitable for medium-size and long-chain aliphatic model substrates. The recent applications of this metathesis reaction to fatty acid derivatives to generate fatty nitriles and bifunctional products are considered. They represent very attractive transformations for the access to N-containing monomers and functional intermediates for the chemical industry from renewable raw materials

Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

“…Using 0.1 mol% of catalyst 12 and 23 were obtained in 73% and 66% yields, respectively (Scheme 11). These first results demonstrate that the transformation of methyl ricinoleate is more difficult to perform than cross-metathesis of diester 8, thus illustrating the inhibition presented by the homoallylic alcohol functionality with respect to a simple internal alkene [14,53]. An alternative route for the production of the fatty diesters was explored by the cross-metathesis of methyl ricinoleate 22 with methyl acrylate, for the production of the diester 24 (89%) with concomitant formation of hydroxyl ester 25 (85%), which is a potential precursor of the fatty diol by hydrogenation (Scheme 11).…”

“…Cross-metathesis of acrylonitrile and unsaturated acids or esters, associated with the further hydrogenation of both the C=C and CN bonds, constitutes a potential strategic way for the production of polyamides [14,15] (Scheme 2). The first example of cross-metathesis of terminal olefins with acrylonitrile was described with the Schrock catalyst Mo(=CHCMe 2 Ph)(NAr)(OCMe(CF 3 ) 2 ), Ar = 2,6-diisopropylphenyl, affording moderate yields [45].…”

“…Vegetable oils by transesterification easily release unsaturated fatty esters which offer, via cross-metathesis with alkenes, selective access to terminal alkenes or bifunctional internal olefins that are crucial intermediates for industry. Thus catalytic crossmetathesis has become a key to reveal the potential of renewable plant oils or natural terpenes [11][12][13][14][15][16][17][18].…”

Cross metathesis of bio-sourced fatty nitriles with acrylonitrile

“…Another important cross metathesis partner that allows further transformation into amines is acrylonitrile [29]. It has been considered for a long time as a reluctant substrate for cross metathesis and has been applied for fats and oils transformations only when ruthenium catalysts bearing a chelating benzylidene carbene ligand appeared [30,31].…”

Plant‐Oil‐Based Polyamides and Polyurethanes: Toward Sustainable Nitrogen‐Containing Thermoplastic Materials

“…In principle, AB‐monomers for linear polyamide synthesis can be obtained via olefin cross‐metathesis of 1 – 3 with suitably functionalized olefins. The cross‐metathesis of 1 with allyl chloride or acrylonitrile would thus give 12‐aminododecanoic acid 6 (after subsequent nucleophilic substitution and hydrogenation or hydrogenation, respectively), but the actual renewable PA 12 synthesis via this route has not been described ( Scheme ). The formed ethylene should not be considered as waste, as it could be, at least in large scale production, recovered and used for other purposes.…”