Synthesis of 3- and 6-sulfonylindoles from ortho-alkynyl-N-sulfonylanilines by the use of Lewis acidic transition-metal catalysts.
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 degrees 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 degrees 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.
Nakamura
Itaru
I
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza Aoba, Aoba-ku, Sendai, 980-8578, Japan. itaru-n@mail.tains.tohoku.ac.jp
Yamagishi
Uichiro
U
Song
Dschun
D
Konta
Sayaka
S
Yamamoto
Yoshinori
Y
D000143:Acids / Q000737:chemistry*; D000478:Alkylation; D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D007211:Indoles / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D028561:Transition Elements / Q000737:chemistry*
C526941:6-sulfonylindole; D000143:Acids; D000814:Aniline Compounds; D007211:Indoles; D028561:Transition Elements; C023650:aniline