Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen‐Centered Polycyclic π‐System Comprising 5‐ and 7‐Membered Rings. (24th August 2022)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Angewandte Chemie. Volume 134:Number 39(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-24
• Subjects: Dehydrogenation -- Density Functional Calculations -- Nitrogen Heterocycles -- Polycyclic Systems -- Reaction Mechanism; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202205287
• Languages: English
• ISSNs: 0044-8249

Abstract

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. Abstract : A new type of nitrogen‐centered polycyclic scaffold with a unique combination of 5‐, 6‐, and 7‐membered rings and appealing properties was synthesized through 3‐fold oxidative cyclodehydrogenation of tri(1‐naphthyl)amine. Theoretical mechanistic studies suggested the formation of this unusual compound to occur under kinetic control via a dicationic mechanism.