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Unsaturated Dodecahedranes - Synthesis of the Highly Pyramidalized, Highly Reactive C20H18 and C20H16 Olefins#

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Methodological alternatives for the preparation of highly strained, highly pyramidalized dodecahedrene 2 (Estr = 87.3 kcal mol-1; Ø = 43.5°, MM2) and 1,16-dodecahedradiene 3 (Estr = 105.3 kcal mol-1; Ø = 42.9°, MM2) have been explored, protection/deprotection strategies have been tested - with the eye on their utilization for the generation of higher unsaturated dodecahedranes (e.g. 1,4,16-triene 4, 1,4,10(14),16-tetraene 5). For the acquisition of preparative quantities of monoene 2 the "P2F" catalyzed cisβ-elimination in bromododecahedrane, of diene 3 the FVP fragmentation of a "twofold protected" precursor (bis-furan adduct) have become the protocols of choice, which both profit from the recent synthetic advances along the pagodane → dodecahedrane scheme. Because of unusually effective steric protection the highly tilted C=C double bonds of 2 (λmax (CH3CN) = 254 nm, νc=c = 1658 cm-1, δc=c = 164.4) and 3 (δc=c = 170.5) enter into thermal stabilization pathways (dimerization, oligomerization) only at higher temperatures (for 2 ca. 50% consumption after 5 h at 100°C in a 3•10-3 molar toluene solution); extreme sensitivity to oxygen is primarily attributed to kinetically and thermodynamically promoted allylic hydrogen abstraction.

Affiliations: 1: Chemisches Laboratorium der Universität Freiburg, Institut für Organische Chemie und Biochemie, Albertstr. 21, D-79104 Freiburg i. Br.


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