Molecular modeling of ring-opening cross metathesis. Distributions of products for the ethenolysis of cis,cis-cycloocta-1,5-diene and cis,cis-1,5-dimethyl-cycloocta-1,5-diene

Tlenkopatchev, Mikhail A.; Vargas, Sergio; Fomine, Serguei

doi:10.1016/s0040-4020(02)00449-0

Cited by 9 publications

(6 citation statements)

References 25 publications

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“…The proportions of different linear dienes and cyclooctadiene at equilibrium were evaluated by using molecular modeling for the ethenolysis of cis , cis ‐cycloocta‐1,5‐diene and cis , cis ‐1,5‐dimethylcycloocta‐1,5‐diene . Ethenolysis of cyclooctene to give 1,9‐decadiene was achieved with high selectivity under 20 atm of ethylene for 20 h at room temperature, with the molybdenum catalyst Mo2 (Scheme ) reaching a turnover number (TON) of 22 500 corresponding to 75 % conversion and 75 % yield of 1,9‐decadiene .…”

Section: Applications In Fine Chemistrymentioning

confidence: 98%

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

Bidange

Fischmeister

Bruneau

2016

Chemistry A European J

120

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Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross-metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon-carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications.

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Section: Applications In Fine Chemistrymentioning

confidence: 98%

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

Bidange

Fischmeister

Bruneau

2016

Chemistry A European J

120

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“…[45] The proportions of different linear dienes and cyclooctadiene at equilibrium were evaluated by using molecular modeling for the ethenolysis of cis,cis-cycloocta-1,5-dienea nd cis,cis-1,5-dimethylcycloocta-1,5-diene. [46] Ethenolysis of cyclooctene to give 1,9-decadienew as achieved with high selectivity under 20 atm of ethylene for 20 ha tr oomt emperature, with the molybdenum catalyst Mo2 (Scheme 4) reaching aturnover number (TON) of 22 500 corresponding to 75 %c onversion and7 5% yield of 1,9-decadiene. [47] With the same catalyst, under 20 atm of ethylene, ethenolysis of cyclopentene gave 1,6-heptadiene in 79 %y ield (TON = 3950 from as ubstrate/catalyst ratio of 5000).…”

Section: Ethenolysis Of Strained and Small Rings:formation Of Dienesmentioning

confidence: 99%

ChemInform Abstract: Ethenolysis: A Green Catalytic Tool to Cleave Carbon—Carbon Double Bonds

2016

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“…It is seen that ROMP of COD in the presence of DCE as a CTA (COD/DME = 1 or 2) proceeds with high selectivity to yield trans,trans,trans-1,10-dicarbomethoxy-deca-1,5,9-triene and monomeric trans,trans-1,6-dicarbomethoxy-hexa-1,5-diene. The concentration of hexa-1,5-diene at equilibrium with COD, trans-C 10 and ethylene is 46 mol%. The calculations are in agreement with experimental data on the ethenolysis of COD by rhenium based catalysts [20].…”

Section: Computational Detailsmentioning

confidence: 99%

“…[9]. We have studied the distributions of cyclic and linear products for the ring-opening cross-metathesis of cis,cis-cycloocta-1,5-diene (COD) and cis,cis-1,5-dimethyl-cycloocta-1,5-diene with ethylene (ethenolysis) using the ab initio approach [10][11][12]. ROMP of cycloolefins in the presence of functionalized olefins as CTAs yields end-functionalized polymers (telechelics) (scheme 1).…”

Section: Introductionmentioning

confidence: 99%