Ring Cleavage for Ring Construction: Oxidative Heterocyclic Segregation toward Tribenzophenanthrolines
Intramolecular double C─N bond formation followed by deselenylation enables a one-pot skeletal editing of selenadiazole-fused naphthoquinodimethanes into previously unknown tribenzophenanthroline derivatives, which serve as precursors to fluorescent metal complexes. This transformation involves the disappearance of the original selenadiazole ring containing two nitrogen atoms and the concurrent formation of two new pyridine rings, each containing a single nitrogen atom. This "heterocyclic segregation (Het-Seg)" reaction is triggered by two-electron oxidation of sterically congested quinodimethane substrates with a folded geometry. The resulting twisted dicationic intermediates are crucial for driving the unique skeletal reorganization.
Authors
- Kota Asai (ORCID: https://orcid.org/0000-0003-3315-157X)
- Yusuke Ishigaki (ORCID: https://orcid.org/0000-0001-7961-3595)
- Takanori Suzuki (ORCID: https://orcid.org/0000-0002-1230-2044)
- Johnny Hu (ORCID: https://orcid.org/0000-0001-8091-2963)
- Takeru Saito
- Takuya Shimajiri (ORCID: https://orcid.org/0000-0002-4948-2739)
Institutions
- Hokkaido University of Science (JP)
- Centre National de la Recherche Scientifique (FR)
- Hokkaido University (JP)
- Institut de Chimie de Strasbourg (FR)
- University North (HR)
- Université de Strasbourg (FR)
- The University of Tokyo (JP)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-06-19
- DOI
- https://doi.org/10.1002/chem.202501974
- Citations
- 1
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 0.94
Funders
- Ministry of Education, Culture, Sports, Science and Technology
- Hokkaido University
- Japan Society for the Promotion of Science
- Precursory Research for Embryonic Science and Technology