From Pagodanes to Nonpentagonal (Homo)Dodecahedranes--The Undecacyclo- [10.10.0.0~(2, 20).0~(3, 10).0~(4, 19).0~(5, 9).0~(6, 18).0~(7, 15).0~(8, 13). 0~(19, 22) 0~(16, 21)] docosane cage

摘要

Pagodane and (seco)dodecahedrane cage structures allowed the study of unusual electronic phenomena and of unusual molecular species (for example, valence isomeric 4c/3e radical cations and a-bishomoaromatic 4c/2e dications). For the quantification ofthe factors determining the transannular electronic interactions, additional model structures with well-defined molecular dimensions are sought. In the synthetic route presented here, pagodanes A are transformed into unsubstituted and into pairwise symmetrically functionalized bis(homo)dodecahedranes C. This strategy, which in principle is also applicable to hetero analogs, is characterized by twofold cyclization of bissecododecahedranes B, with transcaveally opposed C=X bonds and anti-positioned leaving groups L. and corresponds to, without any mechanistic implication, substitution by the relatively distant X groups.