Diels-Alder reactivities of cycloalkenediones with tetrazine

Brian J. Levandowski, Trevor A. Hamlin, Hannah J. Eckvahl, F. Matthias Bickelhaupt, K. N. Houk

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Quantum chemical calculations were used to investigate the Diels-Alder reactivities for a series of cycloalkenediones with tetrazine. We find that the reactivity trend of cycloalkenediones toward tetrazine is opposite to cycloalkenes. The electrostatic interactions between the cycloalkenediones and tetrazine become more stabilizing as the ring size of the cycloalkenediones increases, resulting in lower activation energies. The origin of the more favorable electrostatic interactions and the accelerated reactivities of larger cycloalkenediones result from a stabilizing CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. The Diels-Alder reactivity trend of cycloalkenediones toward tetrazine is opposite that of cycloalkenes. The increased reactivity of the 5- and 6-membered cycloalkenediones relative to the 4-membered cycloalkenedione is attributed to a stabilizing electrostatic CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. [Figure not available: see fulltext.].

Original languageEnglish
Article number33
Pages (from-to)1-5
Number of pages5
JournalJournal of Molecular Modeling
Volume25
Issue number2
Early online date9 Jan 2019
DOIs
Publication statusPublished - Feb 2019

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Coulomb interactions
Cycloparaffins
reactivity
electrostatics
interactions
methylidyne
trends
Activation energy
activation energy
rings

Keywords

  • Density functional theory
  • Diels-Alder reaction
  • Distortion/interaction-activation strain model
  • Electrostatic interactions
  • Reactivity

Cite this

Levandowski, Brian J. ; Hamlin, Trevor A. ; Eckvahl, Hannah J. ; Bickelhaupt, F. Matthias ; Houk, K. N. / Diels-Alder reactivities of cycloalkenediones with tetrazine. In: Journal of Molecular Modeling. 2019 ; Vol. 25, No. 2. pp. 1-5.
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abstract = "Quantum chemical calculations were used to investigate the Diels-Alder reactivities for a series of cycloalkenediones with tetrazine. We find that the reactivity trend of cycloalkenediones toward tetrazine is opposite to cycloalkenes. The electrostatic interactions between the cycloalkenediones and tetrazine become more stabilizing as the ring size of the cycloalkenediones increases, resulting in lower activation energies. The origin of the more favorable electrostatic interactions and the accelerated reactivities of larger cycloalkenediones result from a stabilizing CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. The Diels-Alder reactivity trend of cycloalkenediones toward tetrazine is opposite that of cycloalkenes. The increased reactivity of the 5- and 6-membered cycloalkenediones relative to the 4-membered cycloalkenedione is attributed to a stabilizing electrostatic CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. [Figure not available: see fulltext.].",
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Diels-Alder reactivities of cycloalkenediones with tetrazine. / Levandowski, Brian J.; Hamlin, Trevor A.; Eckvahl, Hannah J.; Bickelhaupt, F. Matthias; Houk, K. N.

In: Journal of Molecular Modeling, Vol. 25, No. 2, 33, 02.2019, p. 1-5.

Research output: Contribution to JournalArticleAcademicpeer-review

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AU - Houk, K. N.

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N2 - Quantum chemical calculations were used to investigate the Diels-Alder reactivities for a series of cycloalkenediones with tetrazine. We find that the reactivity trend of cycloalkenediones toward tetrazine is opposite to cycloalkenes. The electrostatic interactions between the cycloalkenediones and tetrazine become more stabilizing as the ring size of the cycloalkenediones increases, resulting in lower activation energies. The origin of the more favorable electrostatic interactions and the accelerated reactivities of larger cycloalkenediones result from a stabilizing CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. The Diels-Alder reactivity trend of cycloalkenediones toward tetrazine is opposite that of cycloalkenes. The increased reactivity of the 5- and 6-membered cycloalkenediones relative to the 4-membered cycloalkenedione is attributed to a stabilizing electrostatic CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. [Figure not available: see fulltext.].

AB - Quantum chemical calculations were used to investigate the Diels-Alder reactivities for a series of cycloalkenediones with tetrazine. We find that the reactivity trend of cycloalkenediones toward tetrazine is opposite to cycloalkenes. The electrostatic interactions between the cycloalkenediones and tetrazine become more stabilizing as the ring size of the cycloalkenediones increases, resulting in lower activation energies. The origin of the more favorable electrostatic interactions and the accelerated reactivities of larger cycloalkenediones result from a stabilizing CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. The Diels-Alder reactivity trend of cycloalkenediones toward tetrazine is opposite that of cycloalkenes. The increased reactivity of the 5- and 6-membered cycloalkenediones relative to the 4-membered cycloalkenedione is attributed to a stabilizing electrostatic CH/π interaction that is not present in the reaction of the 4-membered cycloalkenedione. [Figure not available: see fulltext.].

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