The metathesis reaction of vinyl ethers

Thu, Cuc Tran; Bastelberger, Thomas; Höcker, Hartwig

doi:10.1016/0304-5102(85)87035-8

Cited by 14 publications

(4 citation statements)

References 17 publications

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“…The only examples are the ROMP of 2,3-dihydrofuran catalyzed by Cr(dCPh 2 )(CO) 5 33 as well as the ROMP of 2,3,4,5-tetrahydrooxypin-2-yl acetate. 34…”

Section: Chromium-based Initiatorsmentioning

confidence: 99%

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Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials

2000

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“…The only examples are the ROMP of 2,3-dihydrofuran catalyzed by Cr(dCPh 2 )(CO) 5 33 as well as the ROMP of 2,3,4,5-tetrahydrooxypin-2-yl acetate. 34…”

Section: Chromium-based Initiatorsmentioning

confidence: 99%

“…Very few reports on the successful use of chromium carbenes for ROMP have been reported so far. The only examples are the ROMP of 2,3-dihydrofuran catalyzed by Cr(CPh 2 )(CO) 5 as well as the ROMP of 2,3,4,5-tetrahydrooxypin-2-yl acetate …”

Section: Transition-metal Alkylidenes As Initiatorsmentioning

confidence: 99%

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials

2000

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“…Experimentally, ethyl vinyl ether and norbornene are very important as substrates because almost all known catalysts react well with norbornene but only a few catalyze the olefin metathesis of linear olefins 1 and because olefin metathesis of vinyl ethers by first- and second-generation Grubbs initiators is irreversible . The reversibility of olefin metathesis with vinyl ethers has been reported for Cr, W, , and Re carbene complexes. However, these substrates do raise new questions: because even within a small group of catalysts, notably first- and second-generation Grubbs-type catalysts, the behavior in acyclic metathesis toward electron-poor and electron-rich, branched and unbranched olefins is so different that it can be used as part of a synthetic strategy .…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts: The Role of Ligands and Substrates from a Theoretical Perspective

2004

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The reaction mechanism of olefin metathesis by ruthenium carbene catalysts is studied by gradient-corrected density functional calculations (BP86). Alternative reaction mechanisms for the reaction of the "first-generation" Grubbs-type catalyst (PCy(3))(2)Cl(2)Ru=CH(2) (1) for the reaction with ethylene are studied. The most likely dissociative mechanism with trans olefin coordination is investigated for the metathesis reaction between the "first-" and the "second-generation" Grubbs-type catalysts 1 and (H(2)IMes)(PCy(3))Cl(2)Ru=CH(2) (2) with different substrates, ethylene, ethyl vinyl ether, and norbornene, and a profound influence of the substrate is found. In contrast to the degenerate reaction with ethylene, the reactions with ethyl vinyl ether and norbornene are strongly exergonic by 8-15 kcal/mol, and this excess energy is released after passing through the metallacyclobutane structure. While the metallacyclobutane is in a deep potential minimum for degenerate metathesis reactions, the energy barrier for the [2+2] cycloreversion vanishes for the most exergonic reactions. On the free energy surface under typical experimental conditions, the rate-limiting steps for the overall reactions are then either metallacyclobutane formation for 1 or phosphane ligand dissociation for 2.

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“…The concentrated supernatant contained primarily cyclic oligomers, as determined by ESI-MS (Figure S4). These cycles are the unsaturated versions of the 5 n -crown- n series of crown ethers. − …”

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confidence: 99%

Polycondensation of Butenediol: Synthesis of Telechelic 2-Butene-1,4-diol Oligomers

et al. 2011

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The catalytic condensation of cis-2-butene-1,4-diol with CpRu(MQA)(C(3)H(5)) (Cp = cyclopentadienyl, MQA = 4-methoxyquinoline-2-carboxylate) generates poly(2-butenediol), an unsaturated telechelic polyether diol with molecular weights between 400 and 4600 g/mol. This Ru(IV) allyl catalyst enchains 2-butene-1,4-diol primarily as the linear trans-2-butenyl ether (92%) along with vinyl branches (8%). These telechelic oligomers are useful chain extenders and macromonomers, as demonstrated by their use in the synthesis of poly(lactide)-b-poly(butenediol)-b-poly(lactide) triblock copolymers. Model studies support a proposed mechanism involving the formation of Ru(IV) allyl intermediates from allylic alcohols and chain growth by selective nucleophilic displacement at the terminus of the Ru(IV) allyl to generate trans-2-butenyl ether linkages.

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The metathesis reaction of vinyl ethers

Cited by 14 publications

References 17 publications

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials

Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts: The Role of Ligands and Substrates from a Theoretical Perspective

Polycondensation of Butenediol: Synthesis of Telechelic 2-Butene-1,4-diol Oligomers

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