Abstract
The spirocyclic bis[propylenethioacetales] of 1,10-dioxo[2.2]-metacyclophanes and their triple layered homologues (tribenzaspiro-[5.5]undecaphanes)1, 2, 4, and5 represent 2,2-geminally disubstituted 1,3-dithianes, the rotameric state of “phenyl” being fixed and determined by the geometry of the rigid cyclophane system.
With respect to their solution conformation the chair shape of the heterorings as well as the axial preference of the aryl moiety is established.
Analogous results are obtained regarding the conformation of the 2,2-geminally disubstituted 1,3-dioxane3 derived from 1,10-dioxo-[2.2]metacyclophane.
The rotational situation of “phenyl” deviates from a strictly gonal state in all compounds studied.
In comparison with1 the overall geometry of the dimethyl derivative2 exhibits additional distorsions.
These conclusions are drawn by means of an extensive 300 MHz-1H-NMR study including NMDR experiments.
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10. Mitt.:H. Keller undH. Lehner, Ann. Chem. (im Druck).
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Langer, E., Lehner, H. & Anteunis, M.J.O. Gezielte Konformationsänderungen an cyclischen Systemen, 11. Mitt.. Monatshefte für Chemie 109, 719–733 (1978). https://doi.org/10.1007/BF00912788
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DOI: https://doi.org/10.1007/BF00912788