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. 2022 Jun 10;7(25):21860-21867.
doi: 10.1021/acsomega.2c02017. eCollection 2022 Jun 28.

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

José Luis Borioni  1 , María T Baumgartner  1 , Marcelo Puiatti  1 , Liliana B Jimenez  1
Affiliations

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

José Luis Borioni et al. ACS Omega. .

Abstract

Perylene 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 since their radical anions fragment and the necessary binaphthyl dianion could not be formed. On the other hand, 49% of N,N-dimethylperylen-1-amine was obtained starting from the N-substituted 2-binapthyl derivative as a substrate, employing a simpler experimental methodology.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Anionic Cyclodehydrogenation Reaction for the Synthesis of Perylene
Adapted with permission from ref (9b).
Figure 1
Figure 1
2-Substituted-1,1′-binaphthalenes employed as substrates in the anionic cyclodehydrogenation reactions.
Scheme 2
Scheme 2. Proposed Mechanism for the Anionic Cyclodehydrogenation Reaction
Adapted with permission from ref (9b).
Scheme 3
Scheme 3. Profile of Energy for the Ring Closure Reaction of Substrate 1a
The color red is employed to remark path A and blue for path B of Scheme 2. The plots of the total spin density of radical anion (1a•–) and open-shell dianion (1a2–) and the corresponding transition states were added as an inset. All free energy values are expressed in kcal/mol and adjusted at 363 K.
Scheme 4
Scheme 4. Anionic Cyclodehydrogenation Reactions of 1b and 1c
Yields are expressed in relative areas obtained by GC.
Scheme 5
Scheme 5. Anionic Cyclodehydrogenation Reaction of 1d
Percentages are isolated yields. The oxidant agent used in the second step is O2.
Scheme 6
Scheme 6. Proposed Extended Mechanisms Involved in the Anionic Cyclodehydrogenation Reactions Carried out for Substrates 1a–d
See this image and copyright information in PMC

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