Benzoannelated centropolyquinanes. Part IX. Synthesis and conformational behavior of fenestrindans (tetrabenzo[5.5.5.5]fenestranes) with four bridgehead substituents

Kuck, Dietmar; Schuster, Andreas; Krause, Ralph A.

doi:10.1021/jo00011a006

Cited by 57 publications

(39 citation statements)

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“…Unfortunately, nitration of the corresponding "bridgehead-blocked" tetramethylfenestrindane 49 (see Scheme 8) [41] and also of centrohexaindane (3) with of HNO 3 (100 %) and H 2 SO 4 (98 %) did not furnish the desired octanitro and dodecanitro derivatives, respectively; rather, the formation of complex mixtures of partially functionalized analogs was observed. However, both 49 and 3 were converted Six-fold bromination and iodination of tribenzotriquinacene 28 was found to be highly efficient and enabled the subsequent conversion to various new derivatives bearing six other functionalities, such as thioether and nitrile groups, or extended unsaturated residues, including different aryl, vinyl, and acetylene units.…”

Section: Polyfunctionalized Centropolyindanes By Aromatic Substitutionmentioning

confidence: 99%

Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry

Kuck

2006

Pure and Applied Chemistry

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The unique geometrical features and structural potential of the centropolyindanes, a complete family of novel, 3D polycyclic aromatic hydrocarbons, are discussed with respect to the inherent orthogonality of their arene units. Thus, the largest member of the family, centrohexaindane, a topologically nonplanar hydrocarbon, is presented as a "Cartesian hexabenzene", because each of its six benzene units is stretched into one of the six directions of the Cartesian space. This feature is discussed on the basis of the X-ray crystal structures of centrohexaindane and two lower members of the centropolyindane family, viz. the parent tribenzotriquinacenes. Recent progress in multiple functionalization and extension of the indane wings of selected centropolyindanes is reported, including several highly efficient sixand eight-fold C-C cross-coupling reactions. Some particular centropolyindane derivatives are presented, such as the first twelve-fold functionalized centrohexaindane and a tribenzotriquinacene bearing three mutually orthogonal phenanthroline groupings at its molecular periphery. Challenges to further extend the arene peripheries of the tribenzotriquinacenes and fenestrindanes to give, eventually, graphite cuttings bearing a central bowl-or saddle-shaped center are outlined, as is the hypothetical generation of a "giant" nanocube consisting of eight covalently bound tribenzotriquinacene units. Along these lines, our recent discovery of a related, solid-state supramolecular cube, containing eight molecules of a particular tribromotrinitrotribenzotriquinacene of the same absolute configuration, is presented for the first time.

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Section: Polyfunctionalized Centropolyindanes By Aromatic Substitutionmentioning

confidence: 99%

Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry

Kuck

2006

Pure and Applied Chemistry

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“…The Dz symmetry of 2a is unique, since the benzo-annulated fenestrane 14 prefers a structure with S, symmetry in the solid state [20]. Also, the N M R data of 14, bearing four bridgehead substituents are interpreted in terms of two S, conformers which interconvcrt at different rates [21]. Finally.…”

Section: ')mentioning

confidence: 99%

Synthesis and Electron‐Diffraction Structure of all‐cis‐[5.5.5.5]Fenestrane

Brünvoll

Guidetti‐Grept

Hargittai

et al. 1993

Helvetica Chimica Acta

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The efficient synthesis of all-cis-[5.5.5.5]fenestrane (2) from the readily available intermediate 3 allowed the electron-diffraction analysis of 2. This structure analysis revealed long C-C bonds in the central C(C), fragment and a twist-envelope conformation for the four cyclopentane substructures. The four bridgehead H-atoms are in a synclinal rather than an ecliptic position with an approximate D, symmetry of 2. Planarizing distortions are evident from the opposite bond angles at the central C-atom being 116.2 0.5" with the remaining four being 103.7 i 0.2".

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“…This clearly reflects our previous finding that the molecular framework of the fenestrindanes adopt two equivalent and apparently static S 4 -symmetric conformations, rather than a single D 2d -symmetrical one. [8,19] Accordingly, the 13 C NMR spectrum of 8 exhibits nine pairs of resonances for the formally equivalent carbons at the indane junctions, for the eight ortho positions and eight peripheral positions of the fenestrindane core and even for those at the pendant styryl groups. Assignment of the resonances was again achieved by applying two-dimensional NMR techniques (see Exp.…”

Section: Resultsmentioning

confidence: 99%

Multiple Vinylation of Tribenzotriquinacenes and Fenestrindanes at Their Aromatic Peripheries by Use of Nájera’s Catalyst

2005

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Highly efficient six-and eightfold Heck cross-coupling reactions were carried out with two related convex-concave and saddle-shaped hydrocarbons bearing several ortho-dibromo functionalities at the molecular periphery, viz. the hexabromotribenzotriquinacene 3a and the octabromofenestrindane 4a. In contrast to conventional palladium catalysts, use of Nájera's oxime-derived palladacycle catalyst 7 effected exhaustive vinylation with styrene or methyl acrylate in high

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Benzoannelated centropolyquinanes. Part IX. Synthesis and conformational behavior of fenestrindans (tetrabenzo[5.5.5.5]fenestranes) with four bridgehead substituents

Cited by 57 publications

References 1 publication

Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry

Functionalized aromatics aligned with the three Cartesian axes: Extension of centropolyindane chemistry

Synthesis and Electron‐Diffraction Structure of all‐cis‐[5.5.5.5]Fenestrane

Multiple Vinylation of Tribenzotriquinacenes and Fenestrindanes at Their Aromatic Peripheries by Use of Nájera’s Catalyst

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