Dioxopyrrolines. LIII. Stereochemical Pathway of [2 + 2] Photocycloaddition Reaction of 4-Ethoxycarbonyl-5-phenyl-lH-pyrrole-2,3-dione to Cyclic Enol Trimethylsilyl Ethers

Takehiro Sano, Miyuki Hirose, Yoshie Horiguchi, Fumiyuki Kiuchi, Yoshisuke Tsuda

Research output: Contribution to journalArticle

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Abstract

The photocycladdition reaction of the dioxopyrroline 1 to cyclic trimethylsilyloxy olefins was examined. The addition of 3-trimethylsilyloxy-lH-indene and 4-trimethylsilyloxy-l,2-dihydronaphthalene occurred in a regio- and stereoselective manner to give the cis-anti-cis cyclobutanes 3 and 4, respectively. The stereochemical result supported the stereo-selection rule which states that the photocycloaddition of a very polar dioxopyrroline-olefin pair proceeds in an s + s manner via a favored O-endo-π-complex transition. On the other hand, the addition of 1-trimethylsilyloxycyclopentene and l-trimethylsily!oxycyclohexene occurred less stereoselectively, proceeding predominantly in an s + a manner to give the adducts 5a, b, 6a, b, 7a, b, and 12. The results are consistent with the prediction of the stereo-selection rule obtained by assuming that these dioxopyrroline-olefin pairs are polar. The latter cases demonstrate that an increased steric hindrance around the olefin moiety affects the polarity of enone-olefin pair in the transition state.

Original languageEnglish
Pages (from-to)64-72
Number of pages9
JournalChemical and Pharmaceutical Bulletin
Volume41
Issue number1
DOIs
Publication statusPublished - 1993 Jan 1
Externally publishedYes

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Keywords

  • X-ray analysis
  • cyclobutane
  • dioxopyrroline
  • donor-acceptor interaction
  • photocycloaddition
  • stereochemistry

ASJC Scopus subject areas

  • Chemistry(all)
  • Drug Discovery

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