A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction

Abstract

Here we report a general method for the synthesis of polycyclic aromatic dicarboximides (PADIs) by palladium-catalyzed annulation of naphthalene dicarboximide to different types of aromatic substrates. Reaction conditions were optimized by systematic variation of ligand, solvent, and additive. It was shown that solvent has a decisive effect on the yield of the reaction products, and thus 1-chloronaphthalene as solvent afforded the highest yield. By applying the optimized reaction conditions, a broad series of planar carbo- and heterocycle containing PADIs were synthesized in up to 97% yield. Moreover, this approach could be applied to curved aromatic scaffold to achieve the respective bowl-shaped PADI. Two-fold annulation was accomplished by employing arene diboronic esters, affording polycyclic aromatic bis(dicarboximides). The optical and electrochemical properties of this broad series of PADIs were explored as well.

Tetrachlorinated Polycyclic Aromatic Dicarboximides: New Electron‐Poor π‐Scaffolds and NIR Emitters by Palladium‐Catalyzed Annulation Reaction

“…Noteworthy that the use of the regioisomeric anthracene boronic pinacol ester 1 b′ led to a drastic decrease in yield (29 %) of 3 b . This observation is in accordance with our previously proposed mechanistic rationale for the annulation reaction of naphthalene dicarboximides with different PAH derivatives, where we assume that the direct C−H arylation, which follows the Suzuki–Miyaura cross‐coupling in this cascade reaction, proceeds through a Heck‐type mechanism and thus prefers C−C bonds with a pronounced olefinic character . Accordingly, the difference in the yields of 3 b for the regioisomers 1 b and 1 b ′ are reflected by the aromaticity/bond order in anthracene as in regioisomer 1 b the C−H arylation takes place at 1‐position with higher bond order, while in 1 b ′ at 9‐position having a lower bond order …”

“…[4d, 10] Accordingly,t he differencei nt he yields of 3b for the regioisomers 1b and 1b' are reflected by the aromaticity/bond order in anthracene as in regioisomer 1b the CÀHa rylation takes place at 1-positionw ith higherb ond order,w hile in 1b' at 9-position having alower bond order. [10,12] Larger p-extended tetrachlorinated PADIsw ere also obtained by this Pd-catalyzed CÀCc oupling cascade reaction. For instance, perylene boronic ester 1e afforded the quaterrylene dicarboximide derivative 3e in 74 %y ield while coronene boronic ester 1f gave the corresponding annulated product 3f in 62 %y ield, however,ahigher reaction temperature (200 8C) was required for the latter substrate due to low solubility.…”

“…This approach has also been successfully applied for the synthesis of terrylene dicarboximides and esters, the latter compounds have been subsequently converted to dicarboximides by conventional imidization reaction . Very recently, we have shown that under optimized reaction conditions this method can be applied for the synthesis of heteroatom‐doped PADIs . Encouraged by our recent results, we wanted to explore further scope of this Pd‐catalyzed convergent method for the synthesis of more electron‐poor PADIs and thought that annulation of core‐chlorinated perylene dicarboximides, which have not been used in this reaction before, to polycyclic aromatic substrates would lead to a new type of electron‐deficient PADIs with significantly enlarged π‐scaffolds.…”

“…[9] Very recently,w eh ave shown that under optimized reaction conditions this method can be applied for the synthesiso fh eteroatom-doped PADIs. [10] Encouragedb y our recent results, we wantedt oe xplore furthers cope of this Pd-catalyzed convergent method for the synthesis of more electron-poor PADIs and thought that annulation of corechlorinated perylened icarboximides, whichh ave not been used in this reactionb efore,t op olycyclic aromatic substrates would lead to an ew type of electron-deficient PADIs with significantly enlarged p-scaffolds. Here we report, indeed, under optimized reactionc onditions Pd-catalyzedC ÀCc oupling cascade reaction of dibromo-tetrachloro-perylene dicarboximide 2 with differentp olycyclic aromatic boron esters 1a-g afforded ab road series of tetrachlorinated PADIs 3a-g (Table 2), emphasizing on the general scope of this method for the synthesis of PADIs.…”

Synthesis and electronic properties of nitrogen-doped π-extended polycyclic aromatic dicarboximides with multiple redox processes

“…Therefore, in order to develop new organic semiconductors with high mobilities, an in-depth understanding of the molecular structure-charge transport property relationships is required. In this regard, π-conjugated fused-ring systems, such as polycyclic aromatic dicarboximides [4][5][6][7] (PADI) and their heteroatom-doped analogues are emerging classes of semiconducting materials 8 derived from the well-known family of polycyclic aromatic hydrocarbons [9][10][11][12][13] (PAH). These materials have been successfully applied in organic (opto)electronics [14][15][16][17][18] and more recently, as electrodes in energy storage devices due to their remarkable redox behavior.…”