[4+2] Cycloadditions of Seven-Membered-Ring trans-Alkenes: Decreasing Reactivity with Increasing Substitution of the Seven-Membered Ring

John Santucci, Jillian R. Sanzone, K. A. Woerpel

Research output: Contribution to journalArticle

Abstract

The reactivity of trans-oxasilacycloheptenes in [4+2] cycloadditions depends on the substitution pattern on the seven-membered ring. Unhindered trans-alkenes undergo [4+2] cycloadditions with 1,3-diphenylisobenzofuran faster than the most reactive trans-cyclooctene. Increasing the substitution of the seven-membered ring or increasing the electron density of the trans-alkene decreases reactivity with 1,3-dienes in concerted cycloaddition reactions. Although highly substituted trans-alkenes are unreactive in concerted cycloaddition reactions, these alkenes react rapidly in stepwise reactions with diethyl azodicarboxylate (DEAD), an electrophilic diene.

Original languageEnglish (US)
Pages (from-to)2933-2943
Number of pages11
JournalEuropean Journal of Organic Chemistry
Volume2016
Issue number17
DOIs
StatePublished - 2016

Keywords

  • Cycloaddition
  • Cycloalkenes
  • Steric hindrance
  • Strained molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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