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Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings
We describe a new type of nitrogen‐centered polycyclic scaffold comprising a unique combination of 5‐, 6‐, and 7‐membered rings. The compound is accessible through an intramolecular oxidative cyclodehydrogenation of tri(1‐naphthyl)amine. To the best of our knowledge this is the very first example of...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9804279/ https://www.ncbi.nlm.nih.gov/pubmed/35900162 http://dx.doi.org/10.1002/anie.202205287 |
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author | Nebauer, Johannes Neiß, Christian Krug, Marcel Vogel, Alexander Fehn, Dominik Ozaki, Shuhei Rominger, Frank Meyer, Karsten Kamada, Kenji Guldi, Dirk M. Görling, Andreas Kivala, Milan |
author_facet | Nebauer, Johannes Neiß, Christian Krug, Marcel Vogel, Alexander Fehn, Dominik Ozaki, Shuhei Rominger, Frank Meyer, Karsten Kamada, Kenji Guldi, Dirk M. Görling, Andreas Kivala, Milan |
author_sort | Nebauer, Johannes |
collection | PubMed |
description | We describe a new type of nitrogen‐centered polycyclic scaffold comprising a unique combination of 5‐, 6‐, and 7‐membered rings. The compound is accessible through an intramolecular oxidative cyclodehydrogenation of tri(1‐naphthyl)amine. To the best of our knowledge this is the very first example of a direct 3‐fold cyclization of a triarylamine under oxidative conditions. The unusual ring fusion motif is confirmed by X‐ray crystallography and the impact of cyclization on the electronic and photophysical properties is investigated both experimentally and theoretically based on density‐functional theory (DFT) calculations. The formation of the unexpected product is rationalized by detailed mechanistic studies on the DFT level. The results suggest the cyclization to occur under kinetic control via a dicationic mechanism. |
format | Online Article Text |
id | pubmed-9804279 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-98042792023-01-03 Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings Nebauer, Johannes Neiß, Christian Krug, Marcel Vogel, Alexander Fehn, Dominik Ozaki, Shuhei Rominger, Frank Meyer, Karsten Kamada, Kenji Guldi, Dirk M. Görling, Andreas Kivala, Milan Angew Chem Int Ed Engl Research Articles We describe a new type of nitrogen‐centered polycyclic scaffold comprising a unique combination of 5‐, 6‐, and 7‐membered rings. The compound is accessible through an intramolecular oxidative cyclodehydrogenation of tri(1‐naphthyl)amine. To the best of our knowledge this is the very first example of a direct 3‐fold cyclization of a triarylamine under oxidative conditions. The unusual ring fusion motif is confirmed by X‐ray crystallography and the impact of cyclization on the electronic and photophysical properties is investigated both experimentally and theoretically based on density‐functional theory (DFT) calculations. The formation of the unexpected product is rationalized by detailed mechanistic studies on the DFT level. The results suggest the cyclization to occur under kinetic control via a dicationic mechanism. John Wiley and Sons Inc. 2022-08-24 2022-09-26 /pmc/articles/PMC9804279/ /pubmed/35900162 http://dx.doi.org/10.1002/anie.202205287 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Research Articles Nebauer, Johannes Neiß, Christian Krug, Marcel Vogel, Alexander Fehn, Dominik Ozaki, Shuhei Rominger, Frank Meyer, Karsten Kamada, Kenji Guldi, Dirk M. Görling, Andreas Kivala, Milan Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title | Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title_full | Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title_fullStr | Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title_full_unstemmed | Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title_short | Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings |
title_sort | oxidative cyclodehydrogenation of trinaphthylamine: selective formation of a nitrogen‐centered polycyclic π‐system comprising 5‐ and 7‐membered rings |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9804279/ https://www.ncbi.nlm.nih.gov/pubmed/35900162 http://dx.doi.org/10.1002/anie.202205287 |
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