Asymmetric synthesis of the ABCD ring system of daphnilactone B via a tandem, double intramolecular, [4+2]/[3+2] cycloaddition strategy

Scott E Denmark, Son T. Nguyen, Ramil Y. Baiazitov

Research output: Contribution to journalArticle

Abstract

An asymmetric synthesis of the ABCD ring system of daphnilactone B is described. The synthesis features a tandem, double intramolecular, [4+2]/[3+2] cycloaddition of a highly functionalized, enantiomerically enriched nitroalkene to generate a pentacyclic nitroso acetal. The cycloaddition establishes six contiguous stereogenic centers including the critical CD ring junction that bears two quaternary stereogenic centers. Hydrogenolysis of the nitroso acetal followed by amide reduction and cyclization provided the AB rings. The methyl substituent on the A ring was installed in the correct configuration via hydrogenation of an exocyclic olefin in the final step..

Original languageEnglish (US)
Pages (from-to)143-154
Number of pages12
JournalHeterocycles
Volume76
Issue number1
DOIs
StatePublished - Dec 1 2008

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Acetals
Cycloaddition
Cycloaddition Reaction
Hydrogenolysis
Hydrogenation
Cyclization
Alkenes
Amides
daphnilactone B

ASJC Scopus subject areas

  • Analytical Chemistry
  • Pharmacology
  • Organic Chemistry

Cite this

Asymmetric synthesis of the ABCD ring system of daphnilactone B via a tandem, double intramolecular, [4+2]/[3+2] cycloaddition strategy. / Denmark, Scott E; Nguyen, Son T.; Baiazitov, Ramil Y.

In: Heterocycles, Vol. 76, No. 1, 01.12.2008, p. 143-154.

Research output: Contribution to journalArticle

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