Dioxopyrrolines. LIII. Stereochemical pathway of [2+2] photocycloaddition reaction of 4-ethoxycarbonyl-5-phenyl-1H-pyrrole-2,3-dione to cyclic enol trimethylsilyl ethers

T. Sano, M. Hirose, Y. Horiguchi, Fumiyuki Kiuchi, Y. Tsuda

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The photocycloaddition reaction of the dioxopyrroline 1 to cyclic trimethylsilyloxy olefins was examined. The addition of 3-trimethylsilyloxy-1H-indene and 4-trimethylsilyloxy-1,2-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 1-trimethylsilyloxycyclohexene 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
Publication statusPublished - 1993
Externally publishedYes

Fingerprint

Pyrroles
Ethers
Alkenes
Cycloparaffins
Cyclobutanes

ASJC Scopus subject areas

  • Chemistry(all)
  • Organic Chemistry
  • Drug Discovery
  • Pharmacology

Cite this

@article{11ea1148750f4249b145173b0665fc41,
title = "Dioxopyrrolines. LIII. Stereochemical pathway of [2+2] photocycloaddition reaction of 4-ethoxycarbonyl-5-phenyl-1H-pyrrole-2,3-dione to cyclic enol trimethylsilyl ethers",
abstract = "The photocycloaddition reaction of the dioxopyrroline 1 to cyclic trimethylsilyloxy olefins was examined. The addition of 3-trimethylsilyloxy-1H-indene and 4-trimethylsilyloxy-1,2-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 1-trimethylsilyloxycyclohexene 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.",
author = "T. Sano and M. Hirose and Y. Horiguchi and Fumiyuki Kiuchi and Y. Tsuda",
year = "1993",
language = "English",
volume = "41",
pages = "64--72",
journal = "Chemical and Pharmaceutical Bulletin",
issn = "0009-2363",
publisher = "Pharmaceutical Society of Japan",
number = "1",

}

TY - JOUR

T1 - Dioxopyrrolines. LIII. Stereochemical pathway of [2+2] photocycloaddition reaction of 4-ethoxycarbonyl-5-phenyl-1H-pyrrole-2,3-dione to cyclic enol trimethylsilyl ethers

AU - Sano, T.

AU - Hirose, M.

AU - Horiguchi, Y.

AU - Kiuchi, Fumiyuki

AU - Tsuda, Y.

PY - 1993

Y1 - 1993

N2 - The photocycloaddition reaction of the dioxopyrroline 1 to cyclic trimethylsilyloxy olefins was examined. The addition of 3-trimethylsilyloxy-1H-indene and 4-trimethylsilyloxy-1,2-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 1-trimethylsilyloxycyclohexene 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.

AB - The photocycloaddition reaction of the dioxopyrroline 1 to cyclic trimethylsilyloxy olefins was examined. The addition of 3-trimethylsilyloxy-1H-indene and 4-trimethylsilyloxy-1,2-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 1-trimethylsilyloxycyclohexene 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.

UR - http://www.scopus.com/inward/record.url?scp=0027412392&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0027412392&partnerID=8YFLogxK

M3 - Article

VL - 41

SP - 64

EP - 72

JO - Chemical and Pharmaceutical Bulletin

JF - Chemical and Pharmaceutical Bulletin

SN - 0009-2363

IS - 1

ER -