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

(E)-11H-Bisbenzoa]fluorenylidene (E-6) was synthesized by Barton’s double extrusion diazo-thione coupling method from 11H-benzoa]fluoren-11-thione (11) and 11-diazo-11H-benzoa]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=C^11′ 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 C^11′ (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 benzoa]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/H^1′ (8.31 ppm); H¹⁰/H^10′ (δ = 7.20 ppm) and H⁹/H^9′ (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 benzob]annelated isomers E -7 and Z -7.