Synlett 2010(19): 2879-2882  
DOI: 10.1055/s-0030-1259038
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Gold-Catalyzed Stereoselective Synthesis of Di- or Trisubstituted Olefins Possessing a 1,4-Diene Framework via Intramolecular Allylation of Alkynes

Yoshikazu Horino*, Yuichi Nakashima, Ken Hashimoto, Shigeyasu Kuroda*
Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Gofuku 3190, Toyama, 930-8555, Japan
Fax: +81(76)4456819; e-Mail: [email protected]; e-Mail: [email protected];
Further Information

Publication History

Received 12 July 2010
Publication Date:
10 November 2010 (online)

Abstract

The cationic gold(I)-catalyzed reaction of 1-alkynyl-2-allylsilylbenzenes with water results in intramolecular allylation of the alkynes via 7-exo-dig cyclization to give 1,4-dienes in good yield with excellent stereoselectivities.

    References and Notes

  • 1a Durand S. Parrain J.-L. Santelli M. J. Chem. Soc., Perkin Trans. 1  2000,  253 
  • 1b Andrey O. Glanzmann C. Landais Y. Parra-Rapado L. Tetrahedron  1997,  53:  2835 
  • 1c Nicolaou KC. Ramphal JY. Petasis NA. Serhan CN. Angew. Chem. Int. Ed.  1991,  30:  1100 
  • 1d Gadikota RR. Keller AI. Callam CS. Lowary TL. Tetrahedron: Asymmetry  2003,  14:  737 
  • Selected recent examples
  • 2a Akiyama K. Gao F. Hoveyda AH. Angew. Chem. Int. Ed.  2010,  49:  419 
  • 2b Matsubara R. Jamison TF. J. Am. Chem. Soc.  2010,  132:  6880 
  • 2c Moreau B. Wu JY. Ritter T. Org. Lett.  2009,  11:  337 
  • 2d Trost BM. Martos-Redruejo A. Org. Lett.  2009,  11:  1071 
  • Transition-metal-catalyzed allylmetalation, for Al, see:
  • 3a Miller JA. Negishi E.-I. Tetrahedron Lett.  1984,  25:  5863 
  • For Mg:
  • 3b Rein FW. Richey HG. Tetrahedron Lett.  1971,  12:  3777 
  • 3c Okada K. Oshima K. Utimoto K. J. Am. Chem. Soc.  1996,  118:  6076 
  • 3d Tang J. Okada K. Shinokubo H. Oshima K. Tetrahedron  1997,  53:  5061 
  • 3e Anastasia L. Dumond YR. Negishi E.-I. Eur. J. Org. Chem.  2001,  3039 
  • For In:
  • 3f Araki S. Imai A. Shimizu K. Butsugan Y. Tetrahedron Lett.  1992,  33:  2581 
  • 3g Araki S. Imai A. Shimizu K. Yamada M. Mori A. Butsugan Y. J. Org. Chem.  1995,  60:  1841 
  • 3h Fujiwara N. Yamamoto Y. J. Org. Chem.  1997,  62:  2318 
  • 3i Klaps E. Schmid W.
    J. Org. Chem.  1999,  64:  7537 
  • For Sn:
  • 3j Asao N. Matsukawa Y. Yamamoto Y. Chem. Commun.  1996,  1513 
  • 3k Miura K. Itoh D. Hondo T. Saito H. Ito H. Hosomi A. Tetrahedron Lett.  1996,  37:  8539 
  • 3l Matsukawa Y. Asao N. Kitahara H. Yamamoto Y. Tetrahedron  1999,  55:  3779 
  • 3m Shirakawa E. Yamasaki K. Yoshida H. Hiyama T. J. Am. Chem. Soc.  1999,  121:  10221 
  • 3n Shirakawa E. Yoshida H. Nakao Y. Hiyama T. Org. Lett.  2000,  2:  2209 
  • For Zn:
  • 3o Knochel P. Normant JF. Tetrahedron Lett.  1984,  25:  1475 
  • 3p Nishikawa T. Yorimitsu H. Oshima K. Synlett  2004,  1573 
  • Lewis acid catalyzed allylsilylation, see:
  • 4a Yeon SH. Han JH. Hong E. Do Y. Jung IN. J. Organomet. Chem.  1995,  499:  159 
  • 4b Asao N. Yoshikawa E. Yamamoto Y. J. Org. Chem.  1996,  61:  4874 
  • 4c Yoshikawa E. Gevorgyan V. Asao N. Yamamoto Y. J. Am. Chem. Soc.  1997,  119:  6781 
  • 4d Imamura K. Yoshikawa E. Gevorgyan V. Yamamoto Y. J. Am. Chem. Soc.  1998,  120:  5339 
  • 4e Asao N. Tomeba H. Yamamoto Y. Tetrahedron Lett.  2005,  46:  27 
  • 4f Asao N. Yamamoto Y. Bull. Chem. Soc. Jpn.  2000,  73:  1071 
  • Gold-catalyzed reactions of allylsilanes with electrophiles, see:
  • 5a Georgy M. Boucard V. Campagne J.-M. J. Am. Chem. Soc.  2005,  127:  14180 
  • 5b Lin C.-C. Teng T.-M. Odedra A. Liu R.-S. J. Am. Chem. Soc.  2007,  129:  3798 
  • 5c Lin C.-C. Teng T.-M. Tsai C.-C. Liao H.-Y. Liu R.-S. J. Am. Chem. Soc.  2008,  130:  16417 
  • 5d Sawama Y. Sawama Y. Krause N. Org. Lett.  2009,  11:  5034 
  • 6 Allylsilylation of alkenes, see: Motokura K. Matsunaga S. Miyaji A. Sakamoto Y. Baba T. Org. Lett.  2010,  12:  1508 
  • 7a Horino Y. Luzung MR. Toste FD. J. Am. Chem. Soc.  2006,  128:  11364 
  • 7b Park S. Lee D. J. Am. Chem. Soc.  2006,  128:  10664 
  • For general reviews of gold catalysis, see:
  • 8a Jiménez-Núñez E. Echavarren AM. Chem. Commun.  2007,  333 
  • 8b Gorin DJ. Toste FD. Nature (London)  2007,  446:  395 
  • 8c Fürstner A. Davies PW. Angew. Chem. Int. Ed.  2007,  46:  3410 
  • 8d Hashmi ASK. Chem. Rev.  2007,  107:  3180 
  • 8e Gorin DJ. Sherry BD. Toste FD. Chem. Rev.  2008,  108:  3351 
  • 8f Shen HC. Tetrahedron  2008,  64:  3885 
  • 8g Shen HC. Tetrahedron  2008,  64:  7847 
  • 10 In the absence of water, 1 provides 3-allyl-1-silaindenes by a gold-catalyzed intramolecular trans-allylsilylation reaction, see: Matsuda T. Kadowaki S. Yamaguchi Y. Murakami M. Chem. Commun.  2008,  2744 
  • 11a Mayr H. Hagen G. J. Chem. Soc., Chem. Commun.  1989,  91 
  • 11b Bartl J. Steenken S. Mayr H. J. Am. Chem. Soc.  1991,  113:  7710 ; and see also ref. 4c
  • 12a Goto K. Okumura T. Kawashima T. Chem. Lett.  2001,  1258 
  • 12b Denmark SE. Sweis RF. Wehrli D. J. Am. Chem. Soc.  2004,  126:  4865 
  • 13a Hayashi E. Takahashi Y. Itoh H. Yoneda N. Bull. Chem. Soc. Jpn.  1993,  66:  3520 
  • 13b Hachiya I. Moriwaki M. Kobayashi S. Tetrahedron Lett.  1995,  36:  409 
  • 13c Medeiros MR. Narayan RS. MacDougal NT. Schaus S. Porco JA. Org. Lett.  2010,  12:  3222 
  • 15a Luzung MR. Markham JP. Toste FD. J. Am. Chem. Soc.  2004,  126:  10858 
  • 15b Ma S. Yu S. Gu Z. Angew. Chem. Int. Ed.  2005,  45:  200 
  • 15c Belmont P. Parker E. Eur. J. Org. Chem.  2009,  6075 
  • 16a Tamao K. Kumada H. Tetrahedron Lett.  1984,  25:  321 
  • 16b Jones GR. Landais Y. Tetrahedron  1996,  52:  7599 
  • 17 Hashmi ASK. Angew. Chem. Int. Ed.  2010,  49:  2 
9

Use of phenol as a nucleophile in place of water gave a complex mixture.

14

AgNTf2, PtCl2, (PPh3)2PtCl2/2AgNTf2, and Sc(OTf)3 did not show any catalytic activities. Furthermore, background reaction mediated by Tf2NH did not proceed, either.

18

For details, see Supporting Information.

19

Another interesting alternative mechanism for the formation of 2, as suggested by one referee, involves initial formation of 3-allyl-1-silaindenes and their subsequent hydrolysis. Indeed, we have observed the formation of 2 from isolated 3-allyl-1-silaindenes under our reaction conditions. However, we were unable to detect such intermediates when monitoring the reaction of 1 by ¹H NMR spectroscopy (see Supporting Information for further details). Nevertheless, we would like to thank the referee for this suggestion.