Download PDF
Synthesis 2010(24): 4221-4227  
DOI: 10.1055/s-0030-1258306
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Facile Synthesis of 1-Methyl-1H-benzo[b]azepines from 1-Methylquinolinium Iodides and Diazo(trimethylsilyl)methylmagnesium Bromide

Mikio Moritaa, Yoshiyuki Hari*b, Toyohiko Aoyamaa
a Graduate School of Pharmaceutical Sciences, Nagoya City University, 3-1 Tanabe-dori, Mizuho, Nagoya 467-8603, Japan
b Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan
Fax: +81(6)68798201; e-Mail: hari@phs.osaka-u.ac.jp;
Further Information

Publication History

Received 9 August 2010
Publication Date:
18 October 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

The reaction of diazo(trimethylsilyl)methylmagnesium bromide, TMSC(MgBr)N2, with 1-methylquinolinium iodides followed by sequential ring expansion using copper(I) chloride gives 1-methyl-3-(trimethylsilyl)-1H-benzo[b]azepines in moderate to good yields. Moreover, the trimethylsilyl group can be removed or converted into a hydroxy(phenyl)methyl group.

Key words

1H-benzo[b]azepines - diazo(trimethylsilyl)methylmagnesium bromide - quinolinium salts - ring expansion - (trimethylsilyl)diazomethane

    References

  • 1 Hoyt SB. London C. Gorin D. Wyvratt MJ. Fisher MH. Abbadie C. Felix JP. Garcia ML. Li X. Lyons KA. McGowan E. MacIntyre DE. Martin WJ. Priest BT. Ritter A. Smith MM. Warren VA. Williams BS. Kaczorowski GJ. Parsons WH. Bioorg. Med. Chem. Lett.  2007,  17:  4630 
    CrossrefPubMedGoogle Scholar
  • 2 Fabio RD. Micheli F. Baraldi D. Bertani B. Conti N. Forno GD. Feriani A. Donati D. Marchioro C. Messeri T. Missio A. Pasquarello A. Pentassuglia G. Pizzi DA. Provera S. Quaglia AM. Sabbatini FM. Farmaco  2003,  58:  723 
    CrossrefGoogle Scholar
  • 3 Ishihara Y. Hirai K. Miyamoto M. Goto G. J. Med. Chem.  1994,  37:  2292 
    CrossrefGoogle Scholar
  • 4a Davis PD. Neckers DC. Tetrahedron Lett.  1978,  2979 
    Google Scholar
  • 4b Ikeda M. Ohno K. Uno T. Tamura Y. Tetrahedron Lett.  1980,  21:  3403 
    Google Scholar
  • 4c Ikeda M. Ohno K. Takahashi M. Uno T. Tamura Y. J. Chem. Soc., Perkin Trans. 1  1982,  741 
    Google Scholar
  • 4d Motyka LA. Tetrahedron Lett.  1985,  26:  2827 
    Google Scholar
  • 5 Teuber HJ. Emmerich G. Tetrahedron Lett.  1970,  4069 
    CrossrefGoogle Scholar
  • 6 Gonzalez E. Bull. Soc. Chim. Fr.  1993,  130:  143 
    Google Scholar
  • 7 Singh V. Batra S. Eur. J. Org. Chem.  2007,  2970 
    CrossrefGoogle Scholar
  • 8a Yadav JS. Reddy BVS. Gupta MK. Prabhakar A. Jagadeesh B. Chem. Commun.  2004,  2124 
    Google Scholar
  • 8b Gogte VN. More KM. Tilak BD. Indian J. Chem.  1974,  12:  1238 
    Google Scholar
  • 8c Sato Y. Kojima H. Shirai H. J. Org. Chem.  1976,  41:  195 
    Google Scholar
  • 8d Sato Y. Kojima H. Shirai H. J. Org. Chem.  1976,  41:  3325 
    Google Scholar
  • 9 CAUTION! Two deaths were recently reported from the use of TMSCHN2 without proper ventilation; see: Barnhart RW. Dale DJ. Ironside MD. Vogt PF. Org. Process Res. Dev.  2009,  13:  1388 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 10a Shioiri T. Aoyama T. In Advances in the Use of Synthons in Organic Chemistry   Vol. 1:  Dondoni A. JAI Press; London: 1993.  p.51 
    Google Scholar
  • 10b Shioiri T. Aoyama T. In Science of Synthesis, Houben-Weyl Methods of Molecular Transformations   Vol. 4:  Fleming I. Thieme; Stuttgart: 2002.  p.569 
    Google Scholar
  • 11a Ogawa H. Aoyama T. Shioiri T. Synlett  1994,  757 
    Google Scholar
  • 11b Hari Y. Tanaka S. Takuma Y. Aoyama T. Synlett  2003,  2151 
    Google Scholar
  • 11c Tsuchida S. Hari Y. Aoyama T. Heterocycles  2005,  65:  2667 
    Google Scholar
  • 11d Morita M. Hari Y. Iguchi T. Aoyama T. Tetrahedron  2008,  64:  1753 
    Google Scholar
  • Recently, we have established the usability of TMSC(MgBr)N2 in some synthetic reactions; see:
  • 12a Hari Y. Tsuchida S. Aoyama T. Tetrahedron Lett.  2006,  47:  1977 
    Google Scholar
  • 12b Hari Y. Tsuchida S. Sone R. Aoyama T. Synthesis  2007,  3371 
    Google Scholar
  • 12c Hari Y. Date K. Kondo R. Aoyama T. Tetrahedron Lett.  2008,  49:  4965 
    Google Scholar
  • 13 Majetich G. Casares A. Chapman D. Behnke M. J. Org. Chem.  1986,  51:  1745 
    CrossrefGoogle Scholar
  • 15 Ruiz A. Rocca P. Marsais F. Godard A. Queguiner G. Tetrahedron Lett.  1997,  38:  6205 
    Google Scholar
  • 16 Zelichenok A. Burtman V. Zenou N. Yitzchaik S. Bella SD. Mushulam G. Kotler Z. J. Phys. Chem. B  1999,  103:  8702 
    CrossrefGoogle Scholar
  • 17 Hamada Y. Sugiura M. Yakugaku Zasshi  1979,  99:  493 
    Google Scholar
  • 18 Gesto C. De la Cuesta E. Avendano C. Synth. Commun.  1989,  19:  3523 
    CrossrefGoogle Scholar
14

Production of only 8a was observed without the use of 4 Å MS.