Synthesis and Structural Data of Tetrabenzo[8]circulene

• Published in: Chemistry : a European journal 2014-03, Vol.20 (13), p.3705-3711
• Main Authors: Miller, Robert W., Duncan, Alexandra K., Schneebeli, Severin T., Gray, Danielle L., Whalley, Adam C.
• Format: Article
• Language: English
• Subjects: annulation; arenes; Aromaticity; Benzenoids; Chemistry; circulenes; Cycloaddition Reaction; Derivatives; fused-ring systems; Instability; Mathematical analysis; Molecular Structure; Palladium - chemistry; Parents; Polycyclic aromatic hydrocarbons; Polycyclic Aromatic Hydrocarbons - chemical synthesis; Polycyclic Aromatic Hydrocarbons - chemistry; Stability; Stereoisomerism; Synthesis
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201304657

In 1976, the first attempted synthesis of the saddle‐shaped molecule [8]circulene was reported. The next 37 years produced no advancement towards the construction of this complicated molecule. But remarkably, over the last six months, a flurry of progress has been made with two groups reporting independent and strikingly different strategies for the synthesis of [8]circulene derivatives. Herein, we present a third synthetic method, in which we target tetrabenzo[8]circulene. Our approach employs a Diels–Alder reaction and a palladium‐catalyzed arylation reaction as the key steps. Despite calculations describing the instability of [8]circulene, coupled with the reported instability of synthesized derivatives of the parent molecule, the addition of four fused benzenoid rings around the periphery of the molecule provides a highly stable structure. This increased stability over the parent [8]circulene was predicted by using Clar’s theory of aromatic sextets and is a result of the compound becoming fully benzenoid upon incorporation of these additional rings. The synthesized compound exhibits remarkable stability under ambient conditions—even at elevated temperatures—with no signs of decomposition over several months. The solid‐state structure of this compound is significantly twisted compared to the calculated structure primarily as a result of crystal‐packing forces in the solid state. Despite this contortion from the lowest‐energy structure, a range of structural data is presented confirming the presence of localized aromaticity in this large polycyclic aromatic hydrocarbon. Harnessing aromaticity: A new synthesis of tetrabenzo[8]circulene is reported. The calculated and experimental data presented herein indicate a strong correlation with the structure predicted by using Clar's theory of aromaticity, which provides insight into the high stability of this structure when compared to previously synthesized analogues. The saddle‐shaped structure was found to be malleable and results in a highly twisted structure in the solid state (see figure).