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

BORIONI, J.L.; BAUMGARTNER, M. T; PUIATTI, M.; JIMENEZ, LILIANA B.

ACS Omega

ACS Publications

Lugar: Washington; Año: 2022

2470-1343

Perylene derivatives constitute a promising class of compoundswith technological applications mainly due to their optoelectronic properties. Onemechanism proposed to synthesize them, starting from binaphthyl derivatives, isanionic cyclodehydrogenation (under reductive conditions). However, the scopeof this reaction is limited. In the present study, we report a theoretical andexperimental analysis of this particular reaction mechanism for its use in thesynthesis 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 proposedmechanism, we suggest that the cyclization takes place from binaphthyl dianioninstead of its radical anion. This dianion has an open-shell diradical nature, and this could be the species that was detected by EPR inprevious studies. The O-substituted derivatives could not afford the perylene derivatives since their radical anions fragment and thenecessary binaphthyl dianion could not be formed. On the other hand, 49% of N,N-dimethylperylen-1-amine was obtained startingfrom the N-substituted 2-binapthyl derivative as a substrate, employing a simpler experimental methodology