Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers

Wang T, Hou Q-Q, Teng Q-F, Yao X-J, Niu W-X, Cao X-P, Kuck D (2010)
CHEMISTRY-A EUROPEAN JOURNAL 16(41): 12412-12424.

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Abstract
Enantiomerically pure tribenzotriquinacenes (TBTQs) bearing two monofunctionalized aromatic nuclei were synthesized for the first time and their optical properties and absolute configuration determined. A remarkably regioselective bis-formylation of the fully bridgehead methylated parent TBTQ hydrocarbon with MeOCHCl2/TiCl4 afforded a mixture of two C-s-symmetrical (achiral) difunctionalized derivatives together with one C-1-symmetrical (chiral) isomer. Reduction and subsequent column chromatography furnished the three respective benzylic TBTQ dialcohols. Optical resolution of the racemic 2,6-bis(hydroxymethyl) derivative was achieved via the diastereomeric (R)-1,1'-bi-2-naphthol ethers and the absolute configuration of the enantiomers was determined by CD exciton model analysis. The electronic circular dichroism (ECD) spectra and the specific rotation of the enantiomers were found to agree with the results of DFT calculations. Among the C-s-symmetrical isomers, the "proximal" 2,11-dialdehyde and the corresponding benzylic dialcohol were identified by 2D NMR spectroscopy and X-ray crystallographic analysis, respectively, and used as the starting point for the synthesis of several novel dithiametacyclophanes. These include the first "dimeric" tribenzotriquinacene-based cyclophanes bearing the bowls of the two TBTQ units attached to each other in a syn (concave-concave) or anti (convex-concave) configuration. The usefulness of such thiacyclophanes as fluorescent chemosensors for different metal ions is also demonstrated.
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Wang T, Hou Q-Q, Teng Q-F, et al. Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers. CHEMISTRY-A EUROPEAN JOURNAL. 2010;16(41):12412-12424.
Wang, T., Hou, Q. - Q., Teng, Q. - F., Yao, X. - J., Niu, W. - X., Cao, X. - P., & Kuck, D. (2010). Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers. CHEMISTRY-A EUROPEAN JOURNAL, 16(41), 12412-12424.
Wang, T., Hou, Q. - Q., Teng, Q. - F., Yao, X. - J., Niu, W. - X., Cao, X. - P., and Kuck, D. (2010). Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers. CHEMISTRY-A EUROPEAN JOURNAL 16, 12412-12424.
Wang, T., et al., 2010. Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers. CHEMISTRY-A EUROPEAN JOURNAL, 16(41), p 12412-12424.
T. Wang, et al., “Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 16, 2010, pp. 12412-12424.
Wang, T., Hou, Q.-Q., Teng, Q.-F., Yao, X.-J., Niu, W.-X., Cao, X.-P., Kuck, D.: Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers. CHEMISTRY-A EUROPEAN JOURNAL. 16, 12412-12424 (2010).
Wang, Tao, Hou, Qin-Qing, Teng, Qing-Feng, Yao, Xiao-Jun, Niu, Wen-Xue, Cao, Xiao-Ping, and Kuck, Dietmar. “Tribenzotriquinacenes Based on Regioselective Bis-formylation: Optical Resolution and Absolute Configuration of Inherently Chiral Derivatives and Synthesis of the First Cyclophane-Type Tribenzotriquinacene Dimers”. CHEMISTRY-A EUROPEAN JOURNAL 16.41 (2010): 12412-12424.
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68 References

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Benzoanellated Centropolyquinanes, 14. Synthesis of Tribenzotriquinacene by Stereocontrolled Cyclization of Phenyl-SubstitutedCs-Diindans (4bα,9,9aα,10-Tetrahydroindeno[1,2-α]indenes)
Kuck, Chemische Berichte 127(1), 1994
Hexacyclo[4.4.0.02,4.03, 9.05, 7.08, 10]decan, ein überbrücktescis-Trishomobenzol
de, Angewandte Chemie 83(11), 1971
Ein einfacher Zugang zu benzoanellierten Centrotriquinanen
Kuck, Angewandte Chemie 96(7), 1984
Auf dem Wege zu Tribenzoacepentalen: Tribenzotriquinacen, Dihydrotribenzoacepentalendiid und das Tribenzoacepentalen-Radikalanion
Kuck, Angewandte Chemie 101(5), 1989
Drei- und vierfach brückenkopfsubstituierte Tribenzotriquinacene
Schuster, Angewandte Chemie 103(12), 1991
Dendrimere: von Generationen zu Funktionalitäten und Funktionen
Issberner, Angewandte Chemie 106(23-24), 1994
Centrohexacyclic or “K5” Molecules: Development of a Growing Family of Topologically Nonplanar Organic Compounds
Kuck, Liebigs Annalen 1997(6), 1997
Cyclotriveratrylenes and cryptophanes: Their synthesis and applications to host-guest chemistry and to the design of new materials
Collet, 1993
The Centropolyindanes and Related Centro-Fused Polycyclic Organic Compounds
Kuck, 1998
Three orthogonal chromophores operating independently within the same molecule.
Langhals H, Rauscher M, Strube J, Kuck D., J. Org. Chem. 73(3), 2008
PMID: 18184004
Novel sulfur-containing amidecrownophanes: synthesis via tandem Claisen rearrangement and an unpredicted mercuration
Seo, Tetrahedron Letters 49(23), 2008
Polyquinanes. A Simple Synthesis of Tricyclo[5.2.1.0(4,10)]deca-2,5,8-triene.
Jacobson, Acta Chemica Scandinavica 21(), 1967
Design and electropolymerization of a new optically active iron tetraspirobifluorenyl porphyrin
PORIEL, Synthetic Metals 158(21-24), 2008
C3v-symmetrical tribenzotriquinacenes as hosts for C60 and C70 in solution and in the solid state.
Georghiou PE, Dawe LN, Tran HA, Strube J, Neumann B, Stammler HG, Kuck D., J. Org. Chem. 73(22), 2008
PMID: 18850747
Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion.
Nishida S, Morita Y, Ueda A, Kobayashi T, Fukui K, Ogasawara K, Sato K, Takui T, Nakasuji K., J. Am. Chem. Soc. 130(45), 2008
PMID: 18937470

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