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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...

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Autores principales: 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
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
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.
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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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