Double-diels-alder approach to maoecrystal V. unexpected C-C bond-forming fragmentations of the [2.2.2]-bicyclic core

Brandon R. Smith, Jon T Njardarson

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Synthetic studies toward maoecrystal V are reported. An oxidative dearomatization/Diels-Alder cascade to assemble the natural product carbocyclic core in one step is proposed. A facile electrocyclization is shown to suppress the intramolecular allene Diels-Alder pathway. This obstacle is alleviated via a stepwise approach with an allene equivalent to access the key cyclopentadiene-fused [2.2.2]-bicyclic core. Upon treatment with Lewis acid, the proposed intramolecular hetero- Diels-Alder reaction is cleanly and unexpectedly diverted either via C-C bond-forming fragmentation to the spiro-indene product (when R = OMe) or via elimination (when R = H).

Original languageEnglish (US)
Pages (from-to)5316-5319
Number of pages4
JournalOrganic Letters
Volume19
Issue number19
DOIs
StatePublished - 2017

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fragmentation
indene
Cyclopentanes
Lewis Acids
Diels-Alder reactions
Cycloaddition Reaction
products
Biological Products
elimination
cascades
acids
propadiene
maoecrystal V
Product R

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Double-diels-alder approach to maoecrystal V. unexpected C-C bond-forming fragmentations of the [2.2.2]-bicyclic core. / Smith, Brandon R.; Njardarson, Jon T.

In: Organic Letters, Vol. 19, No. 19, 2017, p. 5316-5319.

Research output: Contribution to journalArticle

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