PDF icon Download PDF
Synthesis 2011(21): 3507-3515  
DOI: 10.1055/s-0030-1260207
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Chemoselective Activation of Trimethylsilyl Enol Ether Functionalities in the Presence of Silyl-Protected Alcohols by Trimethylsilyl-Nonaflyl Exchange

Ekaterina V. Boltukhina, Andrey E. Sheshenev*, Ilya M. Lyapkalo
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 16610 Prague 6, Czech Republic
Fax: +44(20)75945804; e-Mail: a.sheshenev@imperial.ac.uk;
Further Information

Publication History

Received 1 July 2011
Publication Date:
05 September 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

Trimethylsilyl enol ethers bearing trialkylsilyl-protected hydroxy groups were converted into synthetically valuable bifunctional alkenyl nonaflates under the action of nonafluorobutane-1-sulfonyl fluoride combined with potassium fluoride in the presence of catalytic amounts of dibenzo-18-crown-6. The methodology has been demonstrated for structurally diverse substrates possessing various trialkylsilyl-protected hydroxy groups which remained intact during the reaction course.

Key words

biphasic catalysis - crown ether - sulfonylating reagent - trialkylsilyl ethers - alkenyl nonaflates

    References

  • 2a Scott WJ. McMurry JE. Acc. Chem. Res.  1988,  21:  47 
    Search in Google Scholar
  • 2b Ritter K. Synthesis  1993,  735 
  • 2c Cacchi S. Pure Appl. Chem.  1996,  68:  45 
    Search in Google Scholar
  • 2d Brückner R. Suffert J. Synlett  1999,  657 
  • For the Heck reaction, see:
  • 3a Webel M. Reissig H.-U. Synlett  1997,  1141 
  • 3b Bräse S. Synlett  1999,  1654 
  • 3c Lyapkalo IM. Webel M. Reissig H.-U. Eur. J. Org. Chem.  2001,  4189 
  • 3d Lyapkalo IM. Webel M. Reissig H.-U. Synlett  2001,  1293 
  • 3e Lyapkalo IM. Webel M. Reissig H.-U. Eur. J. Org. Chem.  2002,  3646 
  • 3f Högermeier J. Reissig H.-U. Brüdgam I. Hartl H. Adv. Synth. Catal.  2004,  346:  1868 
    Search in Google Scholar
  • 3g Lyapkalo IM. Högermeier J. Reissig H.-U. Tetrahedron  2004,  60:  7721 
    Search in Google Scholar
  • 3h Vogel MAK. Stark CBW. Lyapkalo IM. Adv. Synth. Catal.  2007,  349:  1019 
    Search in Google Scholar
  • For the Negishi reaction, see:
  • 4a Bellina F. Ciucci D. Rossi R. Vergamini P. Tetrahedron  1999,  55:  2103 
    Search in Google Scholar
  • 4b Ye X.-Y. Li Y.-X. Farrelly D. Flynn N. Gu L. Locke KT. Lippy J. O’Malley K. Twamley C. Zhang L. Ryono DE. Zahler R. Hariharan N. Cheng PTW. Bioorg. Med. Chem. Lett.  2008,  18:  3545 
    Search in Google Scholar
  • For the Stille reaction, see:
  • 5a Wada A. Ieki Y. Ito M. Synlett  2002,  1061 
  • 5b Wada A. Ieki Y. Nakamura S. Ito M. Synthesis  2005,  1581 
  • 5c Wada A. Matsuura N. Mizuguchi Y. Nakagawa K. Ito M. Okano T. Bioorg. Med. Chem.  2008,  16:  8471 
    Search in Google Scholar
  • For the Suzuki reaction, see:
  • 6a Högermeier J. Reissig H.-U. Synlett  2006,  2759 
  • 6b Keck D. Muller T. Bräse S. Synlett  2006,  3457 
  • 6c Högermeier J. Reissig H.-U. Chem. Eur. J.  2007,  13:  2410 
    Search in Google Scholar
  • For the Sonogashira reaction, see refs. 5a, 5b and:
  • 7a Suffert J. Eggers A. Scheuplein SW. Brückner R. Tetrahedron Lett.  1993,  34:  4177 
    Search in Google Scholar
  • 7b Okauchi T. Yano T. Fukamachi T. Ichikawa J. Minami T. Tetrahedron Lett.  1999,  40:  5337 
    Search in Google Scholar
  • 7c Lyapkalo IM. Vogel MAK. Angew. Chem. Int. Ed.  2006,  45:  4019 ; Angew. Chem. 2006, 118, 4124
    Search in Google Scholar
  • 7d Högermeier J. Reissig H.-U. Tetrahedron  2007,  63:  8485 
    Search in Google Scholar
  • 7e Uemura M. Yorimitsu H. Oshima K. Tetrahedron  2008,  64:  1829 
    Search in Google Scholar
  • 8 Sudo Y. Shirasaki D. Harada S. Nishida A. J. Am. Chem. Soc.  2008,  130:  12588 
    Search in Google Scholar
  • 9 For iron-catalyzed coupling with arylcopper reagents, see: Dunet G. Knochel P. Synlett  2006,  407 
  • 10 For the Wulff-Stille synthesis of vinylstannanes, see: Shipe WD. Sorensen EJ. J. Am. Chem. Soc.  2006,  128:  7025 
    CrossrefSearch in Google Scholar
  • 11a Hirsch E. Hünig S. Reissig H.-U. Chem. Ber.  1982,  115:  3687 
    Search in Google Scholar
  • 11b Hertenstein U. Hünig S. Reichelt H. Schaller R. Chem. Ber.  1986,  119:  699 
    Search in Google Scholar
  • 11c Zimmer R. Webel M. Reissig H.-U. J. Prakt. Chem./Chem.-Ztg.  1998,  340:  274 ; and references cited therein
    Search in Google Scholar
  • 11d Lyapkalo IM. Webel M. Reissig H.-U. Eur. J. Org. Chem.  2002,  1015 
  • 11e Aulenta F. Reissig H.-U. Synlett  2006,  2993 
  • 12 Högermeier J. Reissig H.-U. Adv. Synth. Catal.  2009,  351:  2747 
    CrossrefSearch in Google Scholar
  • 13 Vogel MAK. Stark CBW. Lyapkalo IM. Synlett  2007,  2907 
    Thieme Connect
  • 15a Nelson TD. Crouch RD. Synthesis  1996,  1031 
  • 15b Crouch RD. Tetrahedron  2004,  60:  5833 
    Search in Google Scholar
  • 16 Schwesinger R. Link R. Wenzl P. Kossek S. Chem. Eur. J.  2006,  12:  438 
    CrossrefSearch in Google Scholar
  • For examples of TMS for alkali metal or acetyl exchange in the presence of TMS-protected hydroxy, see:
  • 17a Gooding OW. J. Org. Chem.  1990,  55:  4209 
    Search in Google Scholar
  • 17b Limat D. Schlosser M. Tetrahedron  1995,  51:  5799 
    Search in Google Scholar
  • 17c Yu W. Jin Z. J. Am. Chem. Soc.  2002,  124:  6576 
    Search in Google Scholar
  • 17d

    For the sole example of enol TMS-Nf exchange in the presence of TMS ether, see ref. 3e.

  • For Hg(OAc)2 or Pd(OAc)2 catalyzed TMS for SiCl3 exchange in TMS enol ethers in the presence of TBS- or TIPS-protected hydroxy, see:
  • 18a Denmark SE. Stavenger RA. Winter SBD. Wong K.-T. Barsanti PA. J. Org. Chem.  1998,  63:  9517 
    Search in Google Scholar
  • 18b Denmark SE. Fujimori S. Synlett  2001,  1024 
  • 18c Denmark SE. Pham SM. Org. Lett.  2001,  3:  2201 
    Search in Google Scholar
  • 18d Denmark SE. Fujimori S. Org. Lett.  2002,  4:  3477 
    Search in Google Scholar
  • 18e Denmark SE. Fujimori S. Pham SM. J. Org. Chem.  2005,  70:  10823 
    Search in Google Scholar
  • 20 Matthews WS. Bares JE. Bartmess JE. Bordwell FG. Cornforth FJ. Drucker GE. Margolin Z. McCallum RJ. McCollum GJ. Vanier NR. J. Am. Chem. Soc.  1975,  97:  7006 
    CrossrefSearch in Google Scholar
  • 21 López I. Rodríguez S. Izquirdo J. González FVJ.
    J. Org. Chem.  2007,  72:  6614 
    CrossrefSearch in Google Scholar
  • 22 Friedrich E. Lutz W. Chem. Ber.  1980,  113:  1245 
    CrossrefSearch in Google Scholar
  • 23 Seo JW. Comninos JS. Chi DY. Kim DW. Carlson KE. Katzenellenbogen JA. J. Med. Chem.  2006,  49:  2496 
    CrossrefSearch in Google Scholar
  • 24 Gassman PG. Bottorff KJ. J. Org. Chem.  1988,  53:  1097 
    CrossrefSearch in Google Scholar
  • 25 Martin VA. Murray DH. Pratt NE. Zhao Y.-b. Albizati KF. J. Am. Chem. Soc.  1990,  112:  6965 
    CrossrefSearch in Google Scholar
  • 26 Weidong L. Jin Q. Jing L. Ying L. Yulin L. J. Chin. Chem. Soc. (Taipei, Taiwan)  1997,  44:  507 
    Search in Google Scholar
  • 27 Bach T. Jödicke K. Wibbeling B. Tetrahedron  1996,  52:  10861 
    CrossrefSearch in Google Scholar
  • 28 Teichmann H. Prey V. Justus Liebigs Ann. Chem.  1970,  732:  121 
    CrossrefSearch in Google Scholar
  • 29 Shibata S, Yamada Y, Ando K, Fukui K, Nakamura I, and Uchida I. inventors; PCT Int. Appl.  WO94/04523.  ; Chem. Abstr. 1995, 122, 31505
1

Current address: Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, UK.

14

Note: The procedure has been extended to the enol derivatives which are not accessible directly from the carbonyl precursors; see ref. 3c.

19

Sulfonylation of the deprotected hydroxy group with NfF leads to the unstable tertiary nonaflate undergoing a number of elimination/carbocation rearrangements.