High conversion and productive catalyst turnovers in cross-metathesis reactions of natural oils with 2-butene

Patel, Jim; Mujcinovic, Selma; Jackson, W. Roy; Robinson, Andrea J.; Serelis, Algirdas K.; Such, Chris

doi:10.1039/b600956e

Cited by 97 publications

(93 citation statements)

References 17 publications

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“…Most of the work on cross-metathesis of oil-derived unsaturated esters with simple alkenes has been carried out using homogeneous ruthenium-based catalysts. In particular, the metathesis of methyl oleate (MO) with ethylene (ethenolysis) and with 2-butene were investigated on Ru complexes [10,11,12]while the cross-metathesis of MO with 1-hexene was studied on homogeneousWCl 6 /(CH 3 ) 4 Sn catalysts [13]. [14,15],but there are no reportson the use of immobilized Ru complexes for promoting the cross-metathesis of MO with olefins.…”

Section: -Introductionmentioning

confidence: 99%

Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene

Zelín

Nieres

Trasarti

et al. 2015

Applied Catalysis A: General

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Section: -Introductionmentioning

confidence: 99%

Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene

Zelín

Nieres

Trasarti

et al. 2015

Applied Catalysis A: General

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“…For example, TONs as high as 470,000 have been achieved with 8 in the CM of MO and 2-butene. [7] The most active catalyst for ethenolysis in the literature to date is cyclic alkyl amino carbene (CAAC) complex 10 (Scheme 2), which has been previously reported to generate a TON of 35,000 in the CM of MO with ethylene. [4],[5] As a result of the lack of a catalyst sufficiently active to produce teminal olefins using ethylene gas, industrial scale ethenolysis is currently accomplished using higher olefins as ethylene surrogates.…”

mentioning

confidence: 99%

Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Remarkably Active Catalysts for Ethenolysis

et al. 2014

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An expanded family of ruthenium metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands is reported. These catalysts exhibited exceptional activity in the ethenolysis of the seed oil derivative methyl oleate. In many cases, TONs >100,000 were achieved, at only 3 ppm catalyst loading. Remarkably, the most active catalyst system was able to achieve a TON of 340,000, at only 1 ppm catalyst loading. This is the first time a series of metathesis catalysts has exhibited such high performance in cross metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable towards the industrial scale production of linear alpha-olefins (LAOs) and other terminal olefin products.

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“…For methyl 5-heptenoate a cis : trans ratio of 17 : 83 was found, matching well with the reported isomer ratios for similar reactions. 13 Accordingly, in the final reaction mixture 2,5-heptadiene (HC7:2) was found to account for 80% of all olefins. All three possible isomers of 2,5-heptadiene were observed with the trans-trans isomer predominating.…”

Section: Resultsmentioning

confidence: 99%

Mid-chain carboxylic acids by catalytic refining of microalgae oil

et al. 2017

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Microalgae oil serves as a feedstock for a biorefinery approach to mid-chain (di-)carboxylic acid esters, currently only accessible via demanding synthetic routes. Via the butenolysis of mono-and poly-unsaturated fatty acids, short-chain unsaturated fatty acid methyl esters and mono-and di-enes were produced in a high selectivity. These olefins were further processed into value added linear mid-chain (di-)carboxylic acid esters via isomerizing alkoxycarbonylation. Model compounds such as eicosapentaenoic acid were used to study the reactions including the screening of metathesis catalysts and to identify all formed products. Notably, eicosapentaenoic acid, a five-fold unsaturated fatty acid relatively abundant in algae, is successfully converted to four equivalents of heptadiene, which was carbonylated to the linear diester (dimethyl azelate). The butenolysis and subsequent isomerizing alkoxycarbonylation were performed on the algae oil extracted from the diatom Phaeodactylum tricornutum. Despite the multicomponent mixture of numerous lipids and non-lipid compounds present in algae oil, high conversion and high selectivity for the desired products were achieved in both reactions. This approach provides access to several carboxylic mono-and di-acid esters of chain length ranging from C6 to C12 (amongst others azelaic acid ester, suberic acid ester and dodecanedioic acid ester), that are in demand but to which access is limited currently, fully based on algae oils as a renewable resource.

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High conversion and productive catalyst turnovers in cross-metathesis reactions of natural oils with 2-butene

Cited by 97 publications

References 17 publications

Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene

Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene

Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Remarkably Active Catalysts for Ethenolysis

Mid-chain carboxylic acids by catalytic refining of microalgae oil

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