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5,11‐Diazadibenzo[ hi , qr ]tetracene: Synthesis, Properties, and Reactivity toward Nucleophilic Reagents
Author(s) -
Fujimoto Keisuke,
Takimoto Satoshi,
Masuda Shota,
Inuzuka Toshiyasu,
Sanada Kazutaka,
Sakamoto Masami,
Takahashi Masaki
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100944
Subject(s) - tetracene , cycloisomerization , chemistry , moiety , reactivity (psychology) , imine , alkyne , nucleophile , iodobenzene , medicinal chemistry , dibenzothiophene , photochemistry , reagent , indazole , stereochemistry , catalysis , organic chemistry , anthracene , medicine , alternative medicine , pathology
5,11‐Diazadibenzo[ hi , qr ]tetracene was synthesized as a new nitrogen‐substituted polycyclic heteroaromatic compound by Pd‐catalyzed cycloisomerization of an alkyne precursor followed by oxidative cyclization with bis(trifluoroacetoxy)iodobenzene. The substitution of imine‐type nitrogen atoms significantly enhanced its electron‐accepting character and facilitated the direct nucleophilic addition of arylamines under strongly basic conditions to afford the desired amino‐substituted products. The introduction of amino groups induced a remarkable red‐shift in their absorption spectra; the tetrasubstituted product exhibited intense near‐infrared absorbing property. Furthermore, the π‐electronic system, which includes a redox‐active 1,4‐diazabutadiene moiety, underwent reversible interconversion to its corresponding reduced form upon reduction with NaBH 4 and aerobic oxidation.