Vinylation: Kinetics and Mechanism of the Methoxide-catalyzed Addition of Methanol to Phenylacetylene<sup>1</sup>

Miller, Sidney I.; Shkapenko, G.

doi:10.1021/ja01624a030

Cited by 25 publications

(11 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The similar result occurred in the theoretical study of pyrrole anion addition to acetylene for both gas phase and DMSO solution 29. These account for a well known Z ‐stereoselectivity of the nucleophilic addition to monosubstituted acetylenes 10. Therefore, the present study is restricted to considering E ‐metoxyethene ion formation in the SP ‐conformation known to be the most stable in both metoxyethene and its anion 30, 31.…”

Section: Resultssupporting

confidence: 78%

See 1 more Smart Citation

A theoretical study of methanol vinylation reaction mechanism

Vitkovskaya

Larionova

Кобычев

et al. 2008

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:The mechanism of base-catalyzed nucleophilic addition of methanol to acetylene triple bond (vinylation) in dimethyl sulfoxide (DMSO) and methanol solution was studied using the MP2/6-311ϩϩG**//B3LYP/6-31G* calculations with solvent effects included via continuum model. The proton abstraction from methanol by nondissociated alkali in DMSO surrounding media to form alkali metal methoxides CH 3 OM (M ϭ Li, Na, K) was found to occur with a negligible activation barrier. The reasons for facilitation of base-catalyzed alcohol vinylation in the DMSO medium are discussed in the light of both poor solvation of methoxide ion and a specific coordination of reactants by nondissociated alkali in the MOH/DMSO mixtures.

show abstract

Section: Resultssupporting

confidence: 78%

“…Miller and Shkapenko 10 have studied the kinetics of the methoxide‐catalyzed addition of methanol to phenylacetylene in the solvents, methanol and dioxane. The reaction appears to be first order in phenylacetylene, first order in methoxide, and zero order in methanol.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of methanol vinylation reaction mechanism

Vitkovskaya

Larionova

Кобычев

et al. 2008

Int J of Quantum Chemistry

View full text Add to dashboard Cite

show abstract

“…Miller and Shkapenko [10] study on the kinetics of the methoxide-catalyzed methanol addition to phenylacetylene indicates that the bonding of alkoxide ion to the acetylene is the rate-determining step, followed by the rapid abstraction of a proton from the alcohol by the carbanion intermediate.…”

Section: Introductionmentioning

confidence: 99%

Methanol vinylation mechanism in the KOH/DMSO/CH₃OH/C₂H₂ system

Vitkovskaya

Larionova

Кобычев

et al. 2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:The reaction mechanism of methanol vinylation with acetylene involving a nondissociated KOH molecule was studied using the MP2/6-311þþG**// HF/6-31þG* approach with the DMSO molecule explicitly included into reaction system. The whole conversion cycle of methanol vinylation including active nucleophile generation, bonding of the latter to the acetylene moiety yielding an intermediate carbanion, final methyl vinyl ether formation, and potassium hydroxide regeneration could be realized in the coordination shell of nondissociated KOH.

show abstract

“…A detailed mechanism of vinylation reaction and the origin of superbase media catalytic activity are not evident up to date. Miller and Shkapenko10 study on the kinetics of the methoxide‐catalyzed methanol addition to phenylacetylene indicates that the bonding of alkoxide ion to the acetylene is the rate‐determining step, followed by the rapid abstraction of a proton from the alcohol by the carbanion intermediate.…”

Section: Introductionmentioning

confidence: 99%

Treatment of an unraveled intracerebral coil

Xie

2010

Cathet Cardio Intervent

View full text Add to dashboard Cite

We describe a case of coil unraveling that occurred during stent-assisted cerebral aneurysm embolization. The unraveled coil was stretched and the loose end was fixed in the external carotid artery by the addition of other coils. Herniation of the loose coil end to the distal part of the vessel with potential vessel occlusion was prevented and no immediate or long-term complication was observed. © 2010 Wiley-Liss, Inc.

show abstract

Vinylation: Kinetics and Mechanism of the Methoxide-catalyzed Addition of Methanol to Phenylacetylene¹

Cited by 25 publications

References 3 publications

A theoretical study of methanol vinylation reaction mechanism

A theoretical study of methanol vinylation reaction mechanism

Methanol vinylation mechanism in the KOH/DMSO/CH₃OH/C₂H₂ system

Treatment of an unraveled intracerebral coil

Contact Info

Product

Resources

About

Vinylation: Kinetics and Mechanism of the Methoxide-catalyzed Addition of Methanol to Phenylacetylene1

Cited by 25 publications

References 3 publications

A theoretical study of methanol vinylation reaction mechanism

A theoretical study of methanol vinylation reaction mechanism

Methanol vinylation mechanism in the KOH/DMSO/CH3OH/C2H2 system

Treatment of an unraveled intracerebral coil

Contact Info

Product

Resources

About

Vinylation: Kinetics and Mechanism of the Methoxide-catalyzed Addition of Methanol to Phenylacetylene¹

Methanol vinylation mechanism in the KOH/DMSO/CH₃OH/C₂H₂ system