AM1 study of the cycloaddition of singlet methylene to butadiene and the vinylcyclopropane rearrangement

Quirante, J.J.; Enríquez, F.; Hernando, José M.

doi:10.1016/0166-1280(92)80092-z

Cited by 7 publications

(3 citation statements)

References 19 publications

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“…The distance separating the two carbon atoms to be joined through the rearrangement to cyclopentene was only 2.648 Å. The calculated activation energy for the isomerization was 63.6−63.8 kcal/mol. , …”

Section: Computational Studies Of the Rearrangementmentioning

confidence: 93%

“…The calculated activation energy for the isomerization was 63.6-63.8 kcal/mol. 82,83 In the 1990s the challenge to computational chemistry posed by the vinylcyclopropane rearrangement, and by other [1,3] carbon sigmatropic shifts, continued to attract persistent attention. In a 1992 review on hydrocarbon pericyclic reactions, the vinylcyclopropane rearrangement was still considered to be geometrically constrained to be suprafacial on the allyl system, while having an option of either retention or inversion at the migrating carbon.…”

Section: Computational Studies Of the Rearrangementmentioning

confidence: 99%

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Thermal Rearrangements of Vinylcyclopropanes to Cyclopentenes

2003

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Section: Computational Studies Of the Rearrangementmentioning

confidence: 93%

Section: Computational Studies Of the Rearrangementmentioning

confidence: 99%

Thermal Rearrangements of Vinylcyclopropanes to Cyclopentenes

2003

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“…Further, the four transition structures in the four cases could well be isometric, deuterium-labeled versions of w x the transition structure for the 1,3 carbon shift as defined geometrically through theoretical work by Quirante, Enrıguez, and Hernando, 94,95 and bý Houk and co-workers 96 :…”

Section: Hypothetical Mechanismmentioning

confidence: 99%

Thermal isomerizations of vinylcyclopropanes to cyclopentenes

Baldwin

1998

J. Comput. Chem.

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Vinylcyclopropane Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

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This reaction is a thermal [1,3]‐sigmatropic carbon shift of vinylcyclopropanes to cyclopentenes and is generally known as a vinylcyclopropane rearrangement, or vinylcyclopropane‐cyclopentene rearrangement. The study finds that this rearrangement can undergo three types of reactions. The experimental evidence shows that the vinylcyclopropane rearrangement to cyclopentene is the dominating reaction because of the heat of formation of cyclopentene is lower than that of vinylcyclopropane, and the activation energy for the vinylcyclopropane rearrangement is lower than that of epimerization. In addition, an extra group on the cyclopropane ring can further lower the activation energy for the vinylcyclopropane rearrangement and an additional group on the vinyl moiety and at the cis ‐position will decrease the reaction rate. Furthermore, the silyl group enhances the reaction rate and stereoselectivity, owing to the hyperconjugation between the carbon‐silyl bond and the vicinal cyclopropane ring orbital. This reaction has very broad application in organic synthesis.

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AM1 study of the cycloaddition of singlet methylene to butadiene and the vinylcyclopropane rearrangement

Cited by 7 publications

References 19 publications

Thermal Rearrangements of Vinylcyclopropanes to Cyclopentenes

Thermal Rearrangements of Vinylcyclopropanes to Cyclopentenes

Thermal isomerizations of vinylcyclopropanes to cyclopentenes

Vinylcyclopropane Rearrangement

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