Isomerizing Olefin Metathesis as a Strategy To Access Defined Distributions of Unsaturated Compounds from Fatty Acids

• Published in: Journal of the American Chemical Society Vol. 134; no. 33; pp. 13716 - 13729
• Main Authors: Ohlmann, Dominik M, Tschauder, Nicole, Stockis, Jean-Pierre, Gooßen, Käthe, Dierker, Markus, Gooßen, Lukas J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22.08.2012
• Subjects: Alkenes - chemistry; Catalysis; Coordination Complexes - chemistry; Fatty Acids - chemistry; Isomerism; Oleic Acids - chemistry; Palladium - chemistry; Ruthenium - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja303822c

The dimeric palladium­(I) complex [Pd­(μ-Br)tBu3P]2 was found to possess unique activity for the catalytic double-bond migration within unsaturated compounds. This isomerization catalyst is fully compatible with state-of-the-art olefin metathesis catalysts. In the presence of bifunctional catalyst systems consisting of [Pd­(μ-Br)tBu3P]2 and NHC–indylidene ruthenium complexes, unsaturated compounds are continuously converted into equilibrium mixtures of double-bond isomers, which concurrently undergo catalytic olefin metathesis. Using such highly active catalyst systems, the isomerizing olefin metathesis becomes an efficient way to access defined distributions of unsaturated compounds from olefinic substrates. Computational models were designed to predict the outcome of such reactions. The synthetic utility of isomerizing metatheses is demonstrated by various new applications. Thus, the isomerizing self-metathesis of oleic and other fatty acids and esters provides olefins along with unsaturated mono- and dicarboxylates in distributions with adjustable widths. The cross-metathesis of two olefins with different chain lengths leads to regular distributions with a mean chain length that depends on the chain length of both starting materials and their ratio. The cross-metathesis of oleic acid with ethylene serves to access olefin blends with mean chain lengths below 18 carbons, while its analogous reaction with hex-3-enedioic acid gives unsaturated dicarboxylic acids with adjustable mean chain lengths as major products. Overall, the concept of isomerizing metatheses promises to open up new synthetic opportunities for the incorporation of oleochemicals as renewable feedstocks into the chemical value chain.