1-Substituted Perylene Derivatives by Anionic Cyclodehydrogenation: Analysis of the Reaction Mechanism

BORIONI, JOSÉ LUIS; BAUMGARTNER, MARÍA T.; PUIATTI, MARCELO; JIMENEZ, LILIANA B.

ACS Omega

American Chemical Society

Año: 2022 vol. 7 p. 21860 - 21860

erylene derivatives constitute a promising class of compounds with technological applications mainly due to their optoelectronic properties. One mechanism proposed to synthesize them, starting from binaphthyl derivatives, is anionic cyclodehydrogenation (under reductive conditions). However, the scope of this reaction is limited. In the present study, we report a theoretical and experimental analysis of this particular reaction mechanism for its use in the synthesis of 1-substituted perylenes. Different substituents at position 2 of 1,1′-binaphthalene were evaluated: -OCH3, -OSi(CH3)2C(CH3)3, and -N(CH3)2. Based on density functional theory (DFT) calculations on the proposed mechanism, we suggest that the cyclization takes place from binaphthyl dianion instead of its radical anion. This dianion has an open-shell diradical nature, and this could be the species that was detected by EPR in previous studies. The O-substituted derivatives could not afford the perylene derivatives sin