Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines

[Image: see text] Pyridyl tetrazines coordinated to metals like rhenium have been shown to be more reactive in [4 + 2] cycloadditions than their uncomplexed counterparts. Using density functional theory calculations, we found a more favorable interaction energy caused by stronger orbital interaction...

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Autores principales: Turlik, Aneta, Houk, K. N., Svatunek, Dennis
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8453624/
https://www.ncbi.nlm.nih.gov/pubmed/34468143
http://dx.doi.org/10.1021/acs.joc.1c01564
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author Turlik, Aneta
Houk, K. N.
Svatunek, Dennis
author_facet Turlik, Aneta
Houk, K. N.
Svatunek, Dennis
author_sort Turlik, Aneta
collection PubMed
description [Image: see text] Pyridyl tetrazines coordinated to metals like rhenium have been shown to be more reactive in [4 + 2] cycloadditions than their uncomplexed counterparts. Using density functional theory calculations, we found a more favorable interaction energy caused by stronger orbital interactions as the origin of this increased reactivity. Additionally, the high regioselectivity is due to a greater degree of charge stabilization in the transition state, leading to the major product.
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spelling pubmed-84536242021-09-22 Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines Turlik, Aneta Houk, K. N. Svatunek, Dennis J Org Chem [Image: see text] Pyridyl tetrazines coordinated to metals like rhenium have been shown to be more reactive in [4 + 2] cycloadditions than their uncomplexed counterparts. Using density functional theory calculations, we found a more favorable interaction energy caused by stronger orbital interactions as the origin of this increased reactivity. Additionally, the high regioselectivity is due to a greater degree of charge stabilization in the transition state, leading to the major product. American Chemical Society 2021-09-01 2021-09-17 /pmc/articles/PMC8453624/ /pubmed/34468143 http://dx.doi.org/10.1021/acs.joc.1c01564 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Turlik, Aneta
Houk, K. N.
Svatunek, Dennis
Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title_full Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title_fullStr Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title_full_unstemmed Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title_short Origin of Increased Reactivity in Rhenium-Mediated Cycloadditions of Tetrazines
title_sort origin of increased reactivity in rhenium-mediated cycloadditions of tetrazines
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8453624/
https://www.ncbi.nlm.nih.gov/pubmed/34468143
http://dx.doi.org/10.1021/acs.joc.1c01564
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