Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen-Centered Polycyclic pi-System Comprising 5-and 7-Membered Rings

Nebauer J, Neiß C, Krug M, Vogel A, Fehn D, Ozaki S, Rominger F, Meyer K, Kamada K, Guldi DM, Görling A, Kivala M (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Book Volume: 61

DOI: 10.1002/anie.202205287

Abstract

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.

Authors with CRIS profile

Involved external institutions

Ruprecht-Karls-Universität Heidelberg Germany (DE) National Institute of Advanced Industrial Science and Technology / 産業技術総合研究所 (AIST) Japan (JP)

How to cite

APA:

Nebauer, J., Neiß, C., Krug, M., Vogel, A., Fehn, D., Ozaki, S.,... Kivala, M. (2022). Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen-Centered Polycyclic pi-System Comprising 5-and 7-Membered Rings. Angewandte Chemie International Edition, 61. https://doi.org/10.1002/anie.202205287

MLA:

Nebauer, Johannes, et al. "Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen-Centered Polycyclic pi-System Comprising 5-and 7-Membered Rings." Angewandte Chemie International Edition 61 (2022).

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