Electrophile-Dependent Reactivity of Lithiated N-Benzylpyrene-1-Carboxamide

Molecules

Anna Makal¹  Janusz Zakrzewski²  Magdalena Ciechańska²  Anna Wrona-Piotrowicz²  Karolina Koprowska² 

[1] Biological and Chemical Research Center, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland;Department of Organic Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, 91-403 Lodz, Poland;

关键词: pyrene carboxamide;    azaolympicene;    lithiation;    carbolithiation;    fluorescence;   

DOI  :  10.3390/molecules27123930

来源: DOAJ

【 摘 要 】

In this paper, we describe the lithiation of N-benzylpyrene-1-carboxamide with RLi-TMEDA. We found that the reaction outcome strongly depends on the electrophile used in the quenching step. The electrophile can be introduced at either the benzylic position or at the C-2 position in the pyrene nucleus. Furthermore, when H⁺ was used as the quencher, the product of the intramolecular carbolithiation of the pyrene K-region was formed. Dehydrogenation of the obtained compound with DDQ allowed the synthesis of a novel nitrogen polycyclic compound with an aza-benzo[c,d]pyrene (azaolympicene) skeleton. Attempts to extend the reaction scope to the amides substituted in the phenyl ring 8a and 8b gave an unexpected result. The reaction of both compounds with BuLi gave 1-valerylpyrene (9) in good yield. Photophysical properties, including absorption spectra, emission spectra and quantum yields of the emission of selected products, were studied and discussed.

【 授权许可】

Unknown