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Naphthologs of overcrowded bistricyclic aromatic enes: (E)-bisbenzo[a]fluorenylidene

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An Erratum to this article was published on 18 September 2014

Abstract

(E)-11H-Bisbenzo[a]fluorenylidene (E-6) was synthesized by Barton’s double extrusion diazo-thione coupling method from 11H-benzo[a]fluoren-11-thione (11) and 11-diazo-11H-benzo[a]fluorene (13). The reaction is probably thermodynamically controlled; in the event that the less stable Z -6 is also formed, it would rapidly undergo Z → E diastereomerization to give E -6. The B3LYP/6-311G(d,p) calculated diastereomerization barrier for Z -6 → E -6 is ΔG 298 = 57.0 kJ/mol (13.6 kcal/mol). The calculated equilibrium constant K eq(E -6 → Z -6) = 92:8 (at 298 K) is indicative of a marked diastereoselectivity of the reaction leading to E -6. The structure of E-6 was established by 1H-NMR and 13C-NMR spectroscopies and by X-ray analysis. PAE E-6 crystallizes in the monoclinic space group C2/c. The unit cell of the crystal structure E -6 contains eight molecules, arranged as four pairs of enantiomers. PAE E -6 adopts a twisted conformation with the pure twist of the central C11=C11′ bond ω = 39°. The dihedral angle ν in E -6 is 60.6°, which is significantly higher than the respective dihedral angle in PAEs Z -6, 2, E -7, Z -7, 14, and 15. The large syn-pyramidalization angles at C11 and C11′ (χ = 12.6° and 14.8°) of E-6 indicates the enhanced strain in the fjord regions of the molecule. The enhanced twist is primarily attributed to the double benzo[a]annelation of the bifluorenylidene moiety at the fjord regions. The B3LYP/6-311G(d,p) calculated structure of E -6 is in a very good agreement with the experimental X-ray structure. PAE E -6 adopts a twisted conformation in solution, with the downfield chemical shift of H1/H1′ (8.31 ppm); H10/H10′ (δ = 7.20 ppm) and H9/H9′ (δ = 6.86 ppm) in E -6 are positioned above the planes of the opposing naphthalene rings. PAEs E -6 and Z -6 are significantly higher in energy than their corresponding benzo[b]annelated isomers E -7 and Z -7.

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Notes

  1. CCDC-891703 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033; email: deposit@ccdc.cam.ac.uk]

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Authors and Affiliations

  1. Organic Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Philadelphia Building, #201/205, Edmond J. Safra Campus, 91904, Jerusalem, Israel

    Naela Assadi, Sergey Pogodin, Shmuel Cohen & Israel Agranat

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  1. Naela Assadi
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  2. Sergey Pogodin
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  3. Shmuel Cohen
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  4. Israel Agranat
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Correspondence to Israel Agranat.

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An erratum to this article is available at http://dx.doi.org/10.1007/s11224-014-0483-6.

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Assadi, N., Pogodin, S., Cohen, S. et al. Naphthologs of overcrowded bistricyclic aromatic enes: (E)-bisbenzo[a]fluorenylidene. Struct Chem 24, 1229–1240 (2013). https://doi.org/10.1007/s11224-012-0146-4

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