6-(2-Haloethyl)-2,2-dimethyl-4H-1,3-dioxins: versatile haloethyl vinyl ketone equivalents for carbocycle construction

Thomas J. Greshock, Raymond Lee Funk

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

6-(2-Iodoethyl)-2,2-dimethyl-4H-1,3-dioxin has been prepared in five steps from ethyl acetoacetate. A variety of enolates were then alkylated with this iodide. The resulting 6-alkyl-4H-1,3-dioxins were either subjected to further transformations and/or heated (or subjected to a Lewis acid) to effect facile retrocycloaddition reactions. The resulting enones were found to smoothly participate in conjugate addition or olefin metathesis reactions to provide various carbocyclic ring systems. Collectively, these examples document the synthetic equivalency of dioxin 2 with iodoethyl vinyl ketone and, moreover, delineate a strategy for accomplishing the sequential reactions with nucleophiles at the β′, followed by the β electrophilic sites.

Original languageEnglish (US)
Pages (from-to)5437-5439
Number of pages3
JournalTetrahedron Letters
Volume47
Issue number31
DOIs
StatePublished - Jul 31 2006

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Dioxins
Ketones
Lewis Acids
Nucleophiles
Alkenes
Iodides

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

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title = "6-(2-Haloethyl)-2,2-dimethyl-4H-1,3-dioxins: versatile haloethyl vinyl ketone equivalents for carbocycle construction",
abstract = "6-(2-Iodoethyl)-2,2-dimethyl-4H-1,3-dioxin has been prepared in five steps from ethyl acetoacetate. A variety of enolates were then alkylated with this iodide. The resulting 6-alkyl-4H-1,3-dioxins were either subjected to further transformations and/or heated (or subjected to a Lewis acid) to effect facile retrocycloaddition reactions. The resulting enones were found to smoothly participate in conjugate addition or olefin metathesis reactions to provide various carbocyclic ring systems. Collectively, these examples document the synthetic equivalency of dioxin 2 with iodoethyl vinyl ketone and, moreover, delineate a strategy for accomplishing the sequential reactions with nucleophiles at the β′, followed by the β electrophilic sites.",
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6-(2-Haloethyl)-2,2-dimethyl-4H-1,3-dioxins : versatile haloethyl vinyl ketone equivalents for carbocycle construction. / Greshock, Thomas J.; Funk, Raymond Lee.

In: Tetrahedron Letters, Vol. 47, No. 31, 31.07.2006, p. 5437-5439.

Research output: Contribution to journalArticle

TY - JOUR

T1 - 6-(2-Haloethyl)-2,2-dimethyl-4H-1,3-dioxins

T2 - versatile haloethyl vinyl ketone equivalents for carbocycle construction

AU - Greshock, Thomas J.

AU - Funk, Raymond Lee

PY - 2006/7/31

Y1 - 2006/7/31

N2 - 6-(2-Iodoethyl)-2,2-dimethyl-4H-1,3-dioxin has been prepared in five steps from ethyl acetoacetate. A variety of enolates were then alkylated with this iodide. The resulting 6-alkyl-4H-1,3-dioxins were either subjected to further transformations and/or heated (or subjected to a Lewis acid) to effect facile retrocycloaddition reactions. The resulting enones were found to smoothly participate in conjugate addition or olefin metathesis reactions to provide various carbocyclic ring systems. Collectively, these examples document the synthetic equivalency of dioxin 2 with iodoethyl vinyl ketone and, moreover, delineate a strategy for accomplishing the sequential reactions with nucleophiles at the β′, followed by the β electrophilic sites.

AB - 6-(2-Iodoethyl)-2,2-dimethyl-4H-1,3-dioxin has been prepared in five steps from ethyl acetoacetate. A variety of enolates were then alkylated with this iodide. The resulting 6-alkyl-4H-1,3-dioxins were either subjected to further transformations and/or heated (or subjected to a Lewis acid) to effect facile retrocycloaddition reactions. The resulting enones were found to smoothly participate in conjugate addition or olefin metathesis reactions to provide various carbocyclic ring systems. Collectively, these examples document the synthetic equivalency of dioxin 2 with iodoethyl vinyl ketone and, moreover, delineate a strategy for accomplishing the sequential reactions with nucleophiles at the β′, followed by the β electrophilic sites.

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