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Regiodivergent (3 + 2) annulation reactions of oxyallyl cations

We report a new method for the regiodivergent dearomative (3 + 2) reaction between 3-substituted indoles and oxyallyl cations. Access to both regioisomeric products is possible and is contingent on the presence or absence of a bromine atom on the substituted oxyallyl cation. In this way, we are able...

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Detalles Bibliográficos
Autores principales: Protich, Zachary, Lowder, Leah L., Hughes, Russell P., Wu, Jimmy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10189855/
https://www.ncbi.nlm.nih.gov/pubmed/37206390
http://dx.doi.org/10.1039/d2sc06999g
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author Protich, Zachary
Lowder, Leah L.
Hughes, Russell P.
Wu, Jimmy
author_facet Protich, Zachary
Lowder, Leah L.
Hughes, Russell P.
Wu, Jimmy
author_sort Protich, Zachary
collection PubMed
description We report a new method for the regiodivergent dearomative (3 + 2) reaction between 3-substituted indoles and oxyallyl cations. Access to both regioisomeric products is possible and is contingent on the presence or absence of a bromine atom on the substituted oxyallyl cation. In this way, we are able to prepare molecules that contain highly-hindered, stereodefined, vicinal, quaternary centers. Detailed computational studies employing energy decomposition analysis (EDA) at the DFT level establishes that regiochemical control arises from either reactant distortion energy or orbital mixing and dispersive forces, depending on the oxyallyl cation. Examination of the Natural Orbitals for Chemical Valence (NOCV) confirms that indole acts as the nucleophilic partner in the annulation reaction.
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spelling pubmed-101898552023-05-18 Regiodivergent (3 + 2) annulation reactions of oxyallyl cations Protich, Zachary Lowder, Leah L. Hughes, Russell P. Wu, Jimmy Chem Sci Chemistry We report a new method for the regiodivergent dearomative (3 + 2) reaction between 3-substituted indoles and oxyallyl cations. Access to both regioisomeric products is possible and is contingent on the presence or absence of a bromine atom on the substituted oxyallyl cation. In this way, we are able to prepare molecules that contain highly-hindered, stereodefined, vicinal, quaternary centers. Detailed computational studies employing energy decomposition analysis (EDA) at the DFT level establishes that regiochemical control arises from either reactant distortion energy or orbital mixing and dispersive forces, depending on the oxyallyl cation. Examination of the Natural Orbitals for Chemical Valence (NOCV) confirms that indole acts as the nucleophilic partner in the annulation reaction. The Royal Society of Chemistry 2023-04-24 /pmc/articles/PMC10189855/ /pubmed/37206390 http://dx.doi.org/10.1039/d2sc06999g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Protich, Zachary
Lowder, Leah L.
Hughes, Russell P.
Wu, Jimmy
Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title_full Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title_fullStr Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title_full_unstemmed Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title_short Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
title_sort regiodivergent (3 + 2) annulation reactions of oxyallyl cations
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10189855/
https://www.ncbi.nlm.nih.gov/pubmed/37206390
http://dx.doi.org/10.1039/d2sc06999g
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