MINDO/3 study of the thermolysis of 2(3H)-furanone

Arenas, Juan F.; Quirante, J.J.; Ramı́rez, Francisco J.

doi:10.1016/0166-1280(89)80030-2

Cited by 4 publications

(1 citation statement)

References 10 publications

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“…A previous MINDO/3 study of the thermolysis of 11 reported a stepwise pathway . For allowed pericyclic reactions, such pathways usually do not persist in higher level ab initio calculations, and the results reported here are no exception.…”

Section: Referencessupporting

confidence: 49%

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹

1997

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A series of eight thermal cheletropic decarbonylations show dramatic differences in reaction pathways and in activation energies depending on the molecular orbital topology, as calculated by using ab initio molecular orbital theory (MP2(FC)/6-31G* optimized geometries and MP4/D95** + ZPE single point energies). The decarbonylations of 3-cyclopentenone (1) and bicyclo[2.2.1]hepta-2,5-diene-7-one (3) are pericyclic, orbital symmetry allowed reactions, but it is argued that the decarbonylation of cyclopropanone (9), although formally orbital symmetry allowed, lacks an energy of concert and thus is “effectively forbidden”. The carbon monoxide produced from 1 is predicted to be formed vibrationally cool and rotationally hot. Fragmentations of 2,3-furandione (5) and 2,3-pyrroledione (7) are pseudopericyclic reactions with two orbital disconnections, proceed via planar transition structures, and have activation energies that are much lower than expected for pericyclic reactions of comparable exothermicity. It will be an experimental challenge to determine if the carbon monoxide product from each of these is formed with little vibrational or rotational excitation as predicted. Fragmentations of 3H-furan-2-one (11), 3-cyclopentene-1,2-dione (13), and 3-methylene-3H-furan-2-one (15) each have a single disconnection. Strong bonding at the orbital disconnection in the transition structure tends to lower the barrier and give the reaction more pseudopericyclic character.

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Section: Referencessupporting

confidence: 49%

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹

1997

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

Quirante

Enríquez

Hernando

1992

Journal of Molecular Structure: THEOCHEM

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Theoretical ab initio study of the thermal decomposition of 3-cyclopentenone

Bencivenni¹,

Ramondo²,

Quirante

1995

Journal of Molecular Structure: THEOCHEM

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MINDO/3 study of the thermolysis of 2(3H)-furanone

Cited by 4 publications

References 10 publications

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹

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

Theoretical ab initio study of the thermal decomposition of 3-cyclopentenone

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MINDO/3 study of the thermolysis of 2(3H)-furanone

Cited by 4 publications

References 10 publications

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?1

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?1

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

Theoretical ab initio study of the thermal decomposition of 3-cyclopentenone

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Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹

Pericyclic and Pseudopericyclic Thermal Cheletropic Decarbonylations: When Can a Pericyclic Reaction Have a Planar, Pseudopericyclic Transition State?¹