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Interplay of Twisting and Folding in Overcrowded Heteromerous Bistricyclic Aromatic Enes

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journal contribution
posted on 03.06.2000 by Amalia Levy, P. Ulrich Biedermann, Israel Agranat
Fluorenylidenexanthenes 57 were synthesized by 2-fold extrusion diazo−thione couplings. 7 exhibited yellow crystals and purple (560 nm) solutions. 1H NMR of 5 and 7 indicated subtle equilibria twisted (t) ⇌ anti-folded (a) major/minor conformations. 13C DNMR of 6 gave ΔGc(enantiomerization/inversion) = 26.5 kJ/mol and ΔGc(E,Z-topomerization) = 82.0 kJ/mol. PM3 calculations of 5 revealed minima a, t, ts (twisted/syn-folded), ΔΔHf° = 0.0, 14.1, 15.6 kJ/mol, and transition states [t-ts], [a-ts], [t], [a-a*], ΔΔHf° = 16.3, 17.4, 82.2, 99.3 kJ/mol.

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