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Synthesis 2002(5): 0635-0647
DOI: 10.1055/s-2002-23539
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of β-Functionalized α,β-Unsaturated Oximes via Silylation of Nitro Compounds [1]

Vitaly M. Danilenkoa, Alexander A. Tishkov*b, Sema L. Ioffe*b, Ilya M. Lyapkaloa, Yury A. Strelenkob, Vladimir A. Tartakovskyb
a Moscow Chemical Lyceum, 4 Tamozheny proezd,109033, Moscow, Russian Federation
Fax: +7(095)3623440; e-Mail: dan@1303.ru;
b N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913, Moscow, Russian Federation
Fax: +7(095)1355328; e-Mail: tishkov@cacr.ioc.ac.ru;
Further Information

Publication History

Received 10 January 2002
Publication Date:
02 April 2002 (online)

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Abstract

A general method for the synthesis of conjugated enoximes 2 via silylation of functionalized aliphatic nitro compounds 1 has been elaborated. The configuration of obtained products has been determined by NMR spectroscopy.

Key words

nitro compounds - elimination - stereoselectivity - silylation - conjugated enoximes

    References

  • Preliminary comunications:
  • 1a Danilenko VM. Ioffe SL. Strelenko YuA. Karpenko NF. Kalinin AV. Tartakovsky VA. Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.)  1987,  2453 
  • 1b Tishkov AA. Lyapkalo IM. Ioffe SL. Strelenko YuA. Tartakovsky VA. Russ. Chem. Bull. (Engl. Transl.)  1997,  205 
  • 2 Tishkov AA. Kozintsev AV. Lyapkalo IM. Ioffe SL. Kachala VV. Strelenko YuA. Tartakovsky VA. Tetrahedron Lett.  1999,  40:  5075 
    CrossrefSearch in Google Scholar
  • 3 Smirnov VO. Tishkov AA. Lyapkalo IM. Ioffe SL. Strelenko YuA. Tartakovsky VA. Russ. Chem. Bull.  2001,  12: in press
    Search in Google Scholar
  • 4a Dilman AD. Tishkov AA. Lyapkalo IM. Ioffe SL. Strelenko YuA. Tartakovsky VA. Synthesis  1998,  181 
    Crossref
  • 4b Dilman AD. Tishkov AA. Lyapkalo IM. Ioffe SL. Kachala VV. Strelenko YuA. Tartakovsky VA. J. Chem. Soc., Perkin Trans. 1  2000,  2926 
    Crossref
  • 5 Ioffe SL. Lyapkalo IM. Tishkov AA. Danilenko VM. Strelenko YuA. Tartakovsky VA. Tetrahedron  1997,  53:  13085 
    CrossrefSearch in Google Scholar
  • 6 Danilenko VM. Strelenko YuA. Karpenko NF. Ioffe SL. Tartakovsky VA. Bull. Acad. Sci. USSR Div. Chem. Sci. (Engl. Transl.)  1989,  1105 
  • 7 For a review of the preparative methods, see: von Schecken O. Apel G. Schwarz HG. Segnitz A. In Methoden der Organischen Chemie (Houben-Weyl)   Part I:  Georg Thieme Verlag; Stuttgart: 1971.  p.181 
    Search in Google Scholar
  • 8a Yukawa Y. Sakai M. Suzuki S. Bull. Chem. Soc. Jpn.  1966,  39:  2266 
    CrossrefSearch in Google Scholar
  • 8b Shinada T. Yoshihara K. Tetrahedron Lett.  1995,  36:  6701 
    CrossrefSearch in Google Scholar
  • 9a Carotti A. Campagna F. Synthesis  1979,  56 
    Crossref
  • 9b Keumi T. Yamamoto T. Saga H. Kitajima H. Bull. Chem. Soc. Jpn.  1981,  54:  1579 
    CrossrefSearch in Google Scholar
  • 9c Fahey JL. Firestone RA. Christensen BG. J. Med. Chem.  1976,  19:  562 
    CrossrefSearch in Google Scholar
  • 9d Brubaker AN. DeRuiter J. Whitmer WL. J. Med. Chem.  1986,  29:  1094 
    CrossrefSearch in Google Scholar
  • 10a Ricardt G. Bull. Soc. Chim. Fr.  1974,  3-4:  615 
    Search in Google Scholar
  • 10b Ricardt G. Couturier D. C. R. Acad. Sci., Ser. C  1977,  284:  191 
    Search in Google Scholar
  • 11a Van Bergen TJ. Kellogg RM. J. Org. Chem.  1971,  36:  1705 
    Search in Google Scholar
  • 11b Tsujimoto N, Mano M, and Tamura Y. inventors; Japanese Patent  7304785.  ; Chem. Abstr. 1973, 78, 147813
  • 12 Wang X. Cheng T. Zhang Y. Jia Q. Mengshen C. Gaodeng Xuexiao Huahue Xuebao  1987,  8:  133 ; Chem. Abstr. 1988,  108, 94444
    Search in Google Scholar
  • 13 Alcazar J. Almena I. Begtrup M. de la Hoz A. J. Chem. Soc., Perkin Trans. 1  1995,  2773 
    Crossref
  • 14a Khalil ZH. Abdel-Hafez AA. Yanni AS. Moharam AM. Bull. Chem. Soc. Jpn.  1988,  61:  4143 
    CrossrefSearch in Google Scholar
  • 14b Kerdesky FAJ. Schmidt SP. Holmes JH. Dyer RD. Carter GW. Brooks DW. J. Med. Chem.  1987,  30:  1177 
    CrossrefSearch in Google Scholar
  • 14c Unterhalt B. Tetrahedron Lett.  1968,  1841 
    Crossref
  • 15a Galinis DL. McKee TC. Pannell LK. Cardellina JH. Boyd MR. J. Org. Chem.  1997,  62:  8968 
    Search in Google Scholar
  • 15b McKee TC. Galinis DL. Pannell LK. Cardellina JH. Laakso J. Ireland CM. Murray L. Capon RJ. J. Org. Chem.  1998,  63:  7805 
    Search in Google Scholar
  • 15c Kim JW. Shin-ya K. Furihata K. Hayakawa Y. Seto H. J. Org. Chem.  1999,  64:  153 
    Search in Google Scholar
  • 15d Suzumura K. Takahashi I. Matsumoto H. Nagai K. Setiawan B. Rantiatmodjo RM. Suzuki K. Nagano N. Tetrahedron Lett.  1997,  63:  7573 
    Search in Google Scholar
  • 16 Franchetti P. Grifantini M. Martelli S. J. Med. Chem.  1975,  18:  839 
    CrossrefSearch in Google Scholar
  • Several approachs to conjugated enoximes have been described:
  • 17a VanEijk PJSS. Reinhoudt DN. Harkema S. Visser R. Recl. Trav. Chim. Pays-Bas  1986,  105 :  103 
    Search in Google Scholar
  • 17b Severin Th. Bruck B. Chem. Ber.  1965,  98:  3847 
    Search in Google Scholar
  • 17c Lerche H. Treiber J. Severin Th. Chem. Ber.  1980,  113:  2796 
    Search in Google Scholar
  • 17d Severin Th. Adhikary P. Brautigam I. Chem. Ber.  1976,  109:  1179 
    Search in Google Scholar
  • 17e Iesce MR. Cermola F. Guitto A. Giordano F. Scarpati R. J. Org. Chem.  1996,  61:  8677 
    Search in Google Scholar
  • 18 Tishkov AA. Lyapkalo IM. Kozincev AV. Ioffe SL. Strelenko YuA. Tartakovsky VA. Eur. J. Org. Chem.  2000,  3229 
    Crossref
  • 20 For the preparation of silyl nitronates with Me3SiCl/Et3N and BSA, see: Torssell K. Zeuthen O. Acta. Chem. Scand.  1978,  B32:  118 
    Search in Google Scholar
  • 21a Feger H. Simchen G. Liebigs Ann. Chem.  1986,  1456 
    Crossref
  • 21b Feger H. Simchen G. Liebigs Ann. Chem.  1986,  428 
    Crossref
  • 22 Hesse M. Meier H. Zeeh B. Spectroskopische Methoden in der Organischen Chemie   Georg Thieme Verlag; Stuttgart: 1995.  p.108 
  • 23 Hesse M. Meier H. Zeeh B. Spectroskopische Methoden in der Organischen Chemie   Georg Thieme Verlag; Stuttgart: 1995.  p.151 
  • 24 Makarenkova LM. Bliznets IV. Ioffe SL. Strelenko YuA. Tartakovsky VA. Russ. Chem. Bull. (Engl. Transl.)  2000,  49:  1261 
    CrossrefSearch in Google Scholar
  • 25 See, for example, data for syn- and anti-isomers of MeCH=NOH: Hesse M. Meier H. Zeeh B. Spectroskopische Methoden in der Organischen Chemie   Georg Thieme Verlag; Stuttgart: 1995.  p.214 
  • 26 Afonin AV. Ushakov IA. Tarasova OA. Shmidt EYu. Michaleva AI. Voronov VK. Russ. J. Org. Chem. (Engl. Transl.)  2000,  36:  1777 
    Search in Google Scholar
  • 27 See, for example, Perlmutter P. Conjugate Addition Reactions in Organic Synthesis   Pergamon; Oxford: 1992.  and references cited therein
  • 28 Dilman AD. Ph.D. Thesis   N. D. Zelinsky Institute of Organic Chemistry; Moscow: 2001. 
  • 29 Gottlieb HE. Kotlyar V. Nudelman A. J. Org. Chem.  1997,  62:  7512 
    CrossrefPubMedSearch in Google Scholar
  • 30 Bruson HA. inventors; U.S. Patent  2390918 (Resinous Products & Chemical Co.).  ; Chem. Abstr. 1946, 40, 2456
  • 31 Bordwell FG. Bartmess JE. J. Org. Chem.  1978,  43:  3101 
    CrossrefSearch in Google Scholar
  • 32 Janowitz A. Vavrecka M. Hesse M. Helv. Chim. Acta  1991,  74:  1352 
    CrossrefSearch in Google Scholar
  • 33 Andruszkiewicz R. Silverman RB. Synthesis  1989,  953 
    Thieme Connect
  • 34 Ono N. Kamimura A. Miyake H. Hamamoto I. Kaji A. J. Org. Chem.  1985,  50:  3692 
    Search in Google Scholar
  • 35 Smirnova AA. Perekalin VV. Cherbakov VA. J. Org. Chem. USSR (Engl. Transl.)  1968,  4:  2245 
    Search in Google Scholar
  • 36 Zen S. Kaji E. Bull. Chem. Soc. Jpn.  1970,  43:  2277 
    Search in Google Scholar
  • 37 Kohler EP. Engelbrecht H. J. Am. Chem. Soc.  1919,  41:  764 
    CrossrefSearch in Google Scholar
19

The formation of nitroso alkenes upon silylation of β-functionalized nitro compounds with BSA has been unambiguously proved before (see Ref. [5] ).