Diastereodifferentiating the [2+2] photocycloaddition of ethylene to arylmenthyl cyclohexenonecarboxylates: Stacking-driven enhancement of the product diastereoselectivity that is correlated with the reactant ellipticity

Ken Tsutsumi, Yuuki Yanagisawa, Akinori Furutani, Tsumoru Morimoto, Kiyomi Kakiuchi, Takehiko Wada, Tadashi Mori, Yoshihisa Inoue

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18 Citations (Scopus)

Abstract

Upon diastereodifferentiating the [2+2] photocycloaddition of ethylene to a series of p-substituted (-)-8-phenylmenthyl cyclohexenonecarboxylates, the diastereoselectivity was critically controlled by the nature of the substituent introduced to the chiral auxiliary, and the p-nitro-substituted substrate afforded the cycloadducts in 90% diastereomeric excess (de) and with 97% isolated yield. Detailed experimental and theoretical conformation analyses revealed that the stacking interaction of the aromatic auxiliary with the cyclohexenone moiety plays the decisive role in determining the substrate conformation and is, therefore, responsible for the dramatic enhancement of the de. Of particular interest, the product de was directly related to the ellipticity of the substrate, enabling us to "predict" the de prior to photoirradiation.

Original languageEnglish
Pages (from-to)7448-7455
Number of pages8
JournalChemistry - A European Journal
Volume16
Issue number25
DOIs
Publication statusPublished - 2010 Jul 5

Keywords

  • Chirality
  • Circular dichroism
  • Diastereoselectivity
  • Ethylene
  • Photocycloaddition

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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