Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Cationic cyclization of 2-alkenyl-1,3-dithiolanes: DiastereoselectiveSynthesis of trans-decalins
Universite de Strasbourg, Faculte de Pharmacie UMR/CNRS 7199, Laboratoire des Systemes Chimiques Fonctionnels, Illkirch, France.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Les Laboratoires Pierre Fabre, Centre de Developpement Chimique et Industriel, Gaillac, France.
Universite de Strasbourg, Faculte de Pharmacie UMR/CNRS 7199, Laboratoire des Systemes Chimiques Fonctionnels, Illkirch, France.
Show others and affiliations
2011 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 76, no 9, 3274-3285 p.Article in journal (Refereed) Published
Abstract [en]

An unprecedented and highly diastereoselective 6-endo-trig cyclization of 2-alkenyl-1,3-dithiolanes has beendeveloped yielding trans-decalins, an important scaffold present in numerous di- and triterpenes. The novelty of this 6-endo-trigc yclization stands in the stepwise mechanism involving 2-alkenyl-1,3-dithiolane, acting as a novel latent initiator. It is suggested that the thioketal opens temporarily under the influence of TMSOTf, triggering the cationic 6-endo-trig cyclization, andcloses after C−C bond formation and diastereoselective protonation to terminate the process. DFT calculations confirm this mechanistic proposal and provide a rationale for the observed diastereoselectivity. The reaction tolerates a wide range of functionalities and nucleophilic partners within the substrate. We have also shown that the one-pot 6-endo-trig cyclization followedby in situ 1,3-dithiolane deprotection afford directly the corresponding ketone. This improvement allowed the achievement of the shortest total synthesis of triptophenolide and the shortest formal synthesis of triptolide.

Place, publisher, year, edition, pages
American Chemical Society , 2011. Vol. 76, no 9, 3274-3285 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-59923DOI: 10.1021/jo2001116OAI: oai:DiVA.org:su-59923DiVA: diva2:432148
Funder
Swedish Research Council
Available from: 2011-08-01 Created: 2011-08-01 Last updated: 2017-12-08Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Santoro, StefanoHimo, Fahmi
By organisation
Department of Organic Chemistry
In the same journal
Journal of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 45 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf