A computational study of the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one and a related species

Retro-Diels-Alder reaction or concerted nucleophilic attack?

Shawn W E Eisenberg, Mark J. Kurth, William H. Fink

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Calculations up to the MP2/6-31G*//HF/3-21G level have been carried out to study the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (1) and 2,2,4-trimethyl-6H-1,3-oxazin-6-one (3). At this level of calculation, the enthalpy of activation for the thermal cycloreversion of dioxinone 1 was found to be 31.3 kcal/mol with zero-point vibrational energy correction. The experimental value for the reaction in solution is 30.4 kcal/mol. The enthalpy of activation for the as of yet unsynthesized oxazinone 3 was found to be 44.2 kcal/mol with zero-point correction. Contrasting with the standard view that the thermal cycloreversion of dioxinone 1 is a retro-Diels-Alder reaction is the structural information from the HF/3-21G-optimized transition state 5 which shows the plane of the acetone dienophile tilted roughly 90° to the plane of the acylketene diene.

Original languageEnglish (US)
Pages (from-to)3736-3742
Number of pages7
JournalJournal of Organic Chemistry
Volume60
Issue number12
StatePublished - 1995

Fingerprint

Dioxins
Enthalpy
Chemical activation
Acetone
Hot Temperature

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

A computational study of the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one and a related species : Retro-Diels-Alder reaction or concerted nucleophilic attack? / Eisenberg, Shawn W E; Kurth, Mark J.; Fink, William H.

In: Journal of Organic Chemistry, Vol. 60, No. 12, 1995, p. 3736-3742.

Research output: Contribution to journalArticle

@article{156dfcbdc2514462835221ab93491445,
title = "A computational study of the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one and a related species: Retro-Diels-Alder reaction or concerted nucleophilic attack?",
abstract = "Calculations up to the MP2/6-31G*//HF/3-21G level have been carried out to study the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (1) and 2,2,4-trimethyl-6H-1,3-oxazin-6-one (3). At this level of calculation, the enthalpy of activation for the thermal cycloreversion of dioxinone 1 was found to be 31.3 kcal/mol with zero-point vibrational energy correction. The experimental value for the reaction in solution is 30.4 kcal/mol. The enthalpy of activation for the as of yet unsynthesized oxazinone 3 was found to be 44.2 kcal/mol with zero-point correction. Contrasting with the standard view that the thermal cycloreversion of dioxinone 1 is a retro-Diels-Alder reaction is the structural information from the HF/3-21G-optimized transition state 5 which shows the plane of the acetone dienophile tilted roughly 90° to the plane of the acylketene diene.",
author = "Eisenberg, {Shawn W E} and Kurth, {Mark J.} and Fink, {William H.}",
year = "1995",
language = "English (US)",
volume = "60",
pages = "3736--3742",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - A computational study of the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one and a related species

T2 - Retro-Diels-Alder reaction or concerted nucleophilic attack?

AU - Eisenberg, Shawn W E

AU - Kurth, Mark J.

AU - Fink, William H.

PY - 1995

Y1 - 1995

N2 - Calculations up to the MP2/6-31G*//HF/3-21G level have been carried out to study the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (1) and 2,2,4-trimethyl-6H-1,3-oxazin-6-one (3). At this level of calculation, the enthalpy of activation for the thermal cycloreversion of dioxinone 1 was found to be 31.3 kcal/mol with zero-point vibrational energy correction. The experimental value for the reaction in solution is 30.4 kcal/mol. The enthalpy of activation for the as of yet unsynthesized oxazinone 3 was found to be 44.2 kcal/mol with zero-point correction. Contrasting with the standard view that the thermal cycloreversion of dioxinone 1 is a retro-Diels-Alder reaction is the structural information from the HF/3-21G-optimized transition state 5 which shows the plane of the acetone dienophile tilted roughly 90° to the plane of the acylketene diene.

AB - Calculations up to the MP2/6-31G*//HF/3-21G level have been carried out to study the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (1) and 2,2,4-trimethyl-6H-1,3-oxazin-6-one (3). At this level of calculation, the enthalpy of activation for the thermal cycloreversion of dioxinone 1 was found to be 31.3 kcal/mol with zero-point vibrational energy correction. The experimental value for the reaction in solution is 30.4 kcal/mol. The enthalpy of activation for the as of yet unsynthesized oxazinone 3 was found to be 44.2 kcal/mol with zero-point correction. Contrasting with the standard view that the thermal cycloreversion of dioxinone 1 is a retro-Diels-Alder reaction is the structural information from the HF/3-21G-optimized transition state 5 which shows the plane of the acetone dienophile tilted roughly 90° to the plane of the acylketene diene.

UR - http://www.scopus.com/inward/record.url?scp=0000473621&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000473621&partnerID=8YFLogxK

M3 - Article

VL - 60

SP - 3736

EP - 3742

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 12

ER -