Cookies Policy

This site uses cookies. By continuing to browse the site you are agreeing to our use of cookies.

I accept this policy

Find out more here

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

No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.

Brill’s MyBook program is exclusively available on BrillOnline Books and Journals. Students and scholars affiliated with an institution that has purchased a Brill E-Book on the BrillOnline platform automatically have access to the MyBook option for the title(s) acquired by the Library. Brill MyBook is a print-on-demand paperback copy which is sold at a favorably uniform low price.

Access this article

+ Tax (if applicable)
Add to Favorites
You must be logged in to use this functionality

image of Research on Chemical Intermediates

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.


Full text loading...


Data & Media loading...

Article metrics loading...



Can't access your account?
  • Tools

  • Add to Favorites
  • Printable version
  • Email this page
  • Subscribe to ToC alert
  • Get permissions
  • Recommend to your library

    You must fill out fields marked with: *

    Librarian details
    Your details
    Why are you recommending this title?
    Select reason:
    Research on Chemical Intermediates — Recommend this title to your library
  • Export citations
  • Key

  • Full access
  • Open Access
  • Partial/No accessInformation