Diels-Alder reactivities of cycloalkenediones with tetrazine

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

doi:10.1007/s00894-018-3909-z

Diels-Alder reactivities of cycloalkenediones with tetrazine

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

^*Corresponding author for this work

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Research output: Contribution to Journal › Article › Academic › peer-review

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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.].

Original language	English
Article number	33
Pages (from-to)	1-5
Number of pages	5
Journal	Journal of Molecular Modeling
Volume	25
DOIs	https://doi.org/10.1007/s00894-018-3909-z
Publication status	Published - 9 Jan 2019

Funding

ESP maps were plotted on the total electron density from the M06-2X/6-31G(d) calculations. (b) Hirshfeld charges (m a.u.) (bottom row, left to right) of Tz and 1–3 computed at M06-2X/TZ2P//M06-2X/6-31G(d) Acknowledgments We thank the National Science Foundation (NSF CHE-1361104), the National Institute of Health (NIH R01GM109078), and the Netherlands Organization for Scientific Research (NWO) for financial support. We thank Dennis Svatunek for helpful discussions and assistance in generating the ESP maps. Computer time was provided by the UCLA Institute for Digital Research and Education (IDRE) on the Hoffman2 supercomputer. We additionally thank SURFsara for use of the Cartesius supercomputer.

Funders	Funder number
National Institute of Health
Netherlands Organization for Scientific Research
National Science Foundation	1764328, CHE-1361104
National Institutes of Health	R01GM109078
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

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

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10.1007/s00894-018-3909-z

Levandowski2019_Diels-AlderReactivitiesOfCycloalkenedionesWithTetrazineFinal published version, 778 KBLicence: Article 25fa Dutch Copyright Act

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title = "Diels-Alder reactivities of cycloalkenediones with tetrazine",

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.].",

keywords = "Density functional theory, Diels-Alder reaction, Distortion/interaction-activation strain model, Electrostatic interactions, Reactivity",

author = "Levandowski, \{Brian J.\} and Hamlin, \{Trevor A.\} and Eckvahl, \{Hannah J.\} and Bickelhaupt, \{F. Matthias\} and Houk, \{K. N.\}",

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AU - Levandowski, Brian J.

AU - Hamlin, Trevor A.

AU - Eckvahl, Hannah J.

AU - Bickelhaupt, F. Matthias

AU - Houk, K. N.

PY - 2019/1/9

Y1 - 2019/1/9

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.].

KW - Density functional theory

KW - Diels-Alder reaction

KW - Distortion/interaction-activation strain model

KW - Electrostatic interactions

KW - Reactivity

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Diels-Alder reactivities of cycloalkenediones with tetrazine

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