140901-49-1Relevant articles and documents
The Pagodane Route to Dodecahedranes Unsaturated (Hyperstable) and Saturated Bissecododecahedranes
Murty, Bulusu A. R. C.,Pinkos, Rolf,Spurr, Paul R.,Fessner, Wolf-Dieter,Lutz, Georg,et al.
, p. 1719 - 1740 (2007/10/02)
In bissecododecahedra-1,10(11)-dienes, the syn-periplanar and unusually proximate arrangement of the ? bonds is responsible for extraordinary physical properties such as strong through-space homoconjugation, low oxidation potentials, and a special reactivity pattern.In pursuit of route B to dodecahedranes, the hyperstability predicted (MM2) for these bissecodienes and the related monoenes has been experimentally verified only for the latter in their resistance towards catalytic hydrogenation.Non-hydrogenative saturation of (3,8-difunctionlized) bissecodienes (3, 8, 13) and monoenes (4, 9, 14) becomes increasingly hampered due to the increased steric congestion on the more spherical molecular surfaces but can be achieved in "high-driving-force" reactions .In contrast, cycloadditive four-, five- (73), and six-membered (76) ring annulation again is limited to monoadditions.The half-cages in the bissecododecahedrane structures provide for remarkable steric steering and protection 2-, lack of hydrazone formation from ketones 58, 89, resistance of syn-bis(acid chloride) 86 towards hydrolysis. Key Words: Bissecododecahedranes, saturated, unsaturated / Homoconjugation / Hyperstability / Addition reactions / Cage effects
