Single-wing Extended Tribenzotriquinacenes via Bowl-shaped Dehydrobenzene and Isobenzofuran Tribenzotriquinacene Derivatives

Abstract

Monoaryne and monoisobenzofuran analogues of a C(3v)-symmetrical tribenzotriquinacene (TBTQ) were generated in situ and trapped with various dienes and dienophiles, respectively. In this way, a series of single-wing extended TBTQ derivatives bearing the bowl-shaped TBTQ unit in different topographical expositions have become accessible. This includes some novel tribenzotriquinacene "dimers", in which two TBTQ bowls are attached in syn- or anti-orientation at the terminal positions of rigid linker units. Several of these compounds have been characterized by both spectroscopy and X-ray structural analysis. The efficient access to the TBTQ "dimers" may lay a useful foundation for further studies of novel container compounds and supramolecular architectures.

Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes

“…"L ee and co-workersu sed these reaction conditions for the key step in their preparationo fn ovel iptycenes (e.g., 121 a,b), [180] while Kuck and co-workers prepared tribenzotriquinacenes (e.g., 122 a-c). [181] Scheme46. Representative derivatives (112a-c)a nd twisted CPHs 114 and decaphenylanthraceneo btained from the deoxygenation of endoxides using zinc dust in aceticacid at reflux.…”

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

“… Parent tribenzotriquinacene (TBTQ, 1 ), the single‐wing‐extended TBTQ derivative 2 28 and the (yet unknown) parent tris(2,3‐tetraceno)triquinacene B . The insert A provides a view along the axis of one indane wing of 1 , illustrating the almost perfect orthogonal orientation of the other two ( α =88 °) 18.…”

“…Whereas various successful directed extensions of the three aromatic wings of the TBTQ system have been reported,17, 18, 24–27 threefold (′′linear′′) extension with acene units has not been achieved yet. By contrast, single‐wing extension was feasible by Diels–Alder methodology involving in situ‐generated TBTQ‐based monoaryne and monoisobenzofuran analogues at low temperature for trapping with various dienes and dienophiles, respectively 28. In this way, the dibenzo[2,3]anthrotriquinacene 2 and several higher single‐wing‐extended congeners including tetracene and pentacene derivatives were synthesized 28.…”

“…By contrast, single‐wing extension was feasible by Diels–Alder methodology involving in situ‐generated TBTQ‐based monoaryne and monoisobenzofuran analogues at low temperature for trapping with various dienes and dienophiles, respectively 28. In this way, the dibenzo[2,3]anthrotriquinacene 2 and several higher single‐wing‐extended congeners including tetracene and pentacene derivatives were synthesized 28. Threefold application of this strategy within the same TBTQ framework appears to be impeded by the poor solubility of such extended structures at low temperatures 17.…”

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anthrotriquinacene 2 and several higher singlewing-extended congeners including tetracene and pentacene derivatives were synthesized. [28] Threefold application of this strategy within the same TBTQ framework appears to be impeded by the poor solubility of such extended structures at low temperatures. [17,29] Therefore, we now pursued an alternative, high-temperature strategy involving a threefold Diels-Alder reaction of TBTQ-based ortho-quinodimethanes with suitable dienophiles.

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