Synthesis of 3-and 6-sulfonylindoles from ortho-alkynyl-N-sulfonylanilines by the use of lewis acidic transition-metal catalysts

Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Yoshinori Yamamoto

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Gold-catalyzed reactions of ortho-alkynyl-N-sulfonylanilines produced the corresponding 3-sulfonylindoles in good to high yields. For example, the reaction of N-mesyl-N-methyl-2-(1-pentynyl)aniline, N-mesyl-N-methyl-2- (phenylethynyl)-aniline, and 2-ethynyl-N-mesyl-N-methylaniline in the presence of 10 mol% of AuBr3 in toluene at 80°C gave 3-mesyl-1-methyl-2- propylindole, 3-mesyl-1-methyl-2-phenylindole, and 3-mesyl-1-methylindole in 95, 92, and 71% yield, respectively. Furthermore, we found that the reactions of 2-alkynyl-6-methoxy-N-sulfonyl-anilines in the presence of indium catalyst (InBr3) afforded the corresponding 6-sulfonylindoles as the major product in good yields. For example, the reaction of 6-methoxy-N-methyl-2-(1- pentynyl)-N-tosylaniline in the presence of 5 mol% of InBr3 in toluene at 80°C gave an 87:13 mixture of 7-methoxy-1-methyl-2-propyl-6- tosylindole and 7-methoxy-1-methyl-2-propyl-3-tosylindole in 95% yield. Most probably, the gold-catalyzed reactions of ortho-alkynyl-N-sulfonylanilines proceed through a [1,3] sulfonyl migration, whereas the indium-catalyzed cyclizations of 2-alkynyl-6-methoxy-N-sulfonylanilines, which produce 6-sulfonylindoles, proceed by an unprecedented [1,7] sulfonyl migration.

Original languageEnglish
Pages (from-to)285-295
Number of pages11
JournalChemistry - An Asian Journal
Volume3
Issue number2
DOIs
Publication statusPublished - 2008 Feb 1

Keywords

  • Addition reactions
  • Gold
  • Indium
  • Indoles
  • Sulfonyl migration

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

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