Diels–Alder Cycloaddition to the Bay Region of Perylene and Its Derivatives as an Attractive Strategy for PAH Core Expansion: Theoretical and Practical Aspects

Abstract

PAHs (polycyclic aromatics hydrocarbons), the compound group that contains perylene and its derivatives, including functionalized ones, have attracted a great deal of interest in many fields of science and modern technology. This review presents all of the research devoted to modifications of PAHs that are realized via the Diels–Alder (DA) cycloaddition of various dienophiles to the bay regions of PAHs, leading to the π-extension of the starting molecule. This type of annulative π-extension (APEX) strategy has emerged as a powerful and efficient synthetic method for the construction of polycyclic aromatic hydrocarbons and their functionalized derivatives, nanographenes, and π-extended fused heteroarenes. Then, [4 + 2] cycloadditions of ethylenic dienophiles, -N=N-, i.e., diazo-dienophiles and acetylenic dienophiles, are presented. This subject is discussed from the organic synthesis point of view but supported by theoretical calculations. The possible applications of DA cycloaddition to PAH bay regions in various science and technology areas, and the prospects for the development of this synthetic method, are also discussed.

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

“…Namely, LUMO for COOMe is located lower, but steric hindrance is higher for Ph than COOMe. Analogically, we observed that the influence of electron and steric factors are quite similar to the DA cycloaddition to the perylene bay region [ 54 , 55 ].…”

“…Again, the highest reactivity of acetylene with two COOMe groups is worth noting. This is undoubtedly the effect of LUMO energy decrease [ 54 , 55 ].…”

“…The reference system for the reactions described in this review can be thermal cycloaddition of alkynes and arynes into perylene bay region—acting as a conjugated diene, with H 2 extrusion. We described known reactions of this type, including mechanistic considerations, in our 2020 [ 54 ] review and our work from 2020 [ 55 ].…”

Recent advances on perylene-based photoinitiators of polymerization

“…[280] In this work, BPTI was the only dye to be prepared by cycloaddition of maleic anhydride to the perylene bay region of perylene diimide. [281,282] Figure 17. Chemical structures of PTCTE, BPTI and DPPDI, the different monomers and additives.…”

Post-synthetic π-extension of perylene conjugated porous polymerviaAPEX reactions: tunable optical and gas storage properties

“…21 When treated with suitable dienophiles in the presence of an oxidative reagent, π-extension takes place. 22 In this context, perylene is the suitable platform for the ODA reaction as it poses two bay positions (Scheme S1, ESI†). When perylene is treated with maleic anhydride in the presence of p -chloranil, π-extended benzoperylene anhydride is obtained in 10 min.…”