Highly Selective Ring-Opening/Cross-Metathesis Reactions of Norbornene Derivatives Using Selenocarbene Complexes as Catalysts

Katayama, Hiroyuki; Urushima, Hideto; Nishioka, Tsuneo; Wada, Chikaya; Nagao, Masato; Ozawa, Fumiyuki

doi:10.1002/1521-3773(20001215)39:24<4513::aid-anie4513>3.0.co;2-c

Cited by 85 publications

(49 citation statements)

References 28 publications

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“…10 It has been adopted as a quenching reagent in ring-opening polymerization (ROMP) to stop the reaction propagation and produce an olefin-capped polymer chain. 11 The Grubbs group reported 12 that the formation of a Fisher carbene by reaction of a large excess of ethyl vinyl ether with both 1st and 2nd generation Grubbs' catalysts is quantitative and irreversible by 1 H NMR spectroscopy.…”

Section: Introductionsupporting

confidence: 64%

Di(ethylene glycol) vinyl ether: a highly efficient deactivating reagent for olefin metathesis catalysts

Liu

Nichols

Smith

2009

Tetrahedron Letters

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Section: Introductionsupporting

confidence: 64%

Di(ethylene glycol) vinyl ether: a highly efficient deactivating reagent for olefin metathesis catalysts

Liu

Nichols

Smith

2009

Tetrahedron Letters

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“…10 A disclosure by Ozawa in 2000 outlines a Ru-catalyzed transformation involving norbornene and phenylvinyl ether; the desired product was obtained in only 17% yield and, notably, with 85% Z selectivity. 11 Subsequent studies by Rainier offer five additional examples of transformations of ethylvinyl ether or enol acetate with 7-oxa- or 7-azanorbornenes, promoted by achiral Ru-based carbenes; nearly equal mixtures of Z and E alkenes were uniformly generated. 12 Thus, to the best of our knowledge, catalytic ROCM or EROCM reactions that involve an enol ether and which proceed with effective control of alkene stereoselectivity and/or enantioselectivity have not been disclosed.…”

Section: Introductionmentioning

confidence: 99%

Enol Ethers as Substrates for Efficient Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Promoted by Stereogenic-at-Mo Complexes: Utility in Chemical Synthesis and Mechanistic Attributes

Ibrahem

Hasegawa

et al. 2012

J. Am. Chem. Soc.

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The first examples of catalytic enantioselective ring-opening/cross-metathesis (EROCM) reactions that involve enol ethers are reported. Specifically, we demonstrate that catalytic EROCM of several oxa- and azabicycles, cyclobutenes and a cyclopropene with an alkyl- or aryl-substituted enol ether proceed readily in the presence of a stereogenic-at-Mo monopyrrolide-monoaryloxide. In some instances, as little as 0.15 mol % of the catalytically active alkylidene is sufficient to promote complete conversion within 10 minutes. The desired products are formed in up to 90% yield and >99:1 enantiomeric ratio (er) with the disubstituted enol ether generated in >90% Z selectivity. The enol ether of the enantiomerically enriched products can be easily differentiated from the terminal alkene through a number of functionalization procedures that lead to the formation of useful intermediates for chemical synthesis (e.g., efficient acid hydrolysis to afford the enantiomerically enriched carboxaldehyde). In certain cases, enantioselectivity is strongly dependent on enol ether concentration: larger equivalents of the cross partner leads to the formation of products of high enantiomeric purity (versus near racemic products with one equivalent). The length of reaction time can be critical to product enantiomeric purity; high enantioselectivity in reactions that proceed to >98% conversion in as brief a reaction time as 30 seconds can be nearly entirely eroded within 30 minutes. Mechanistic rationale that accounts for the above characteristics of the catalytic process is provided.

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“…Failure to do so led to substantial polymerisation of norbornene. The reason for this behaviour is unclear [80].…”

Section: Vinyl Chalcogenidesmentioning

confidence: 99%

Metathesis of heteroatom-substituted olefins and alkynes: Current scope and limitations

Weghe

Bisseret

Blanchard

et al. 2006

Journal of Organometallic Chemistry

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Highly Selective Ring-Opening/Cross-Metathesis Reactions of Norbornene Derivatives Using Selenocarbene Complexes as Catalysts

Abstract: Fischer‐type ruthenium carbene complexes bearing a selanylcarbene ligand efficiently catalyze ring‐opening/cross‐metathesis (ROCM) of norbornene derivatives with phenyl vinyl selenide to give the ROCM products in high selectivities (see scheme).

Cited by 85 publications

References 28 publications

Di(ethylene glycol) vinyl ether: a highly efficient deactivating reagent for olefin metathesis catalysts

Di(ethylene glycol) vinyl ether: a highly efficient deactivating reagent for olefin metathesis catalysts

Enol Ethers as Substrates for Efficient Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Promoted by Stereogenic-at-Mo Complexes: Utility in Chemical Synthesis and Mechanistic Attributes

Metathesis of heteroatom-substituted olefins and alkynes: Current scope and limitations

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