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Synlett 2006(11): 1750-1752  
DOI: 10.1055/s-2006-944222
LETTER
© Georg Thieme Verlag Stuttgart · New York

Carbonyl Propargylation and Allenylation with 2-Propynyl Mesylates, Tin(IV) Iodide, and Tetrabutylammonium Iodide Controlled by Either a Steric Effect or Coordination Effect

Yoshiro Masuyama*, Ryouichi Yamazuki, Masaru Ohtsuka, Yasuhiko Kurusu
Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-ku, Tokyo 102-8554, Japan
Fax: +81(3)32383361; e-Mail: y-masuya@sophia.ac.jp;
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Publication History

Received 22 March 2006
Publication Date:
04 July 2006 (online)

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Abstract

A combination of tin(IV) iodide and tetrabutylammonium iodide can be used for propargylation or allenylation of aldehydes with 2-propynyl mesylates in dichloromethane. 1-Methyl-2-propynyl mesylate or 2-butynyl mesylate results in propargylation or allenylation controlled by the steric effect of the 1- or 3-methyl group, and 3-trimethylsilyl-2-propynyl mesylate results in propargylation controlled by the coordination of triiodostannate to silane.

Key words

nucleophilic addition - propargylation - allenylation - tin(IV) iodide - tetrabutylammonium iodide

    References and Notes

  • 1a Klein J. In The Chemistry of the Carbon-Carbon Triple Bond   Patai S. Wiley; New York: 1978.  p.343 
    Google Scholar
  • 1b Moreau J.-L. In The Chemistry of Ketenes, Allenes, and Related Compounds   Patai S. Wiley; New York: 1980.  p.363 
    Google Scholar
  • 1c Schuster HF. Coppola GM. Allenes in Organic Synthesis   Wiley; New York: 1984. 
    Google Scholar
  • 1d Yamamoto H. In Comprehensive Organic Synthesis   Vol. 2:  Trost MB. Fleming I. Pergamon; Oxford: 1991.  p.81 
    Google Scholar
  • 1e Modern Acetylene Chemistry   Stang PJ. Diederich F. VCH; Weinheim: 1995. 
    Google Scholar
  • 2a Mukaiyama T. Harada T. Chem. Lett.  1981,  621 
    CrossrefGoogle Scholar
  • 2b Boldrini GP. Tagliavini E. Trombini C. Umani-Ronchi A. J. Chem. Soc., Chem. Commun.  1986,  685 
    CrossrefGoogle Scholar
  • 2c Tanaka H. Hamatani T. Yamashita S. Torii S. Chem. Lett.  1986,  1461 
    CrossrefGoogle Scholar
  • 2d Iyoda M. Kanao Y. Nishizaki M. Oda M. Bull. Chem. Soc. Jpn.  1989,  62:  3380 
    CrossrefGoogle Scholar
  • 2e Belyk K. Rozema MJ. Knochel P. J. Org. Chem.  1992,  57:  4074 
    CrossrefGoogle Scholar
  • 2f Yavari I. Riazi-Kermani F. Synth. Commun.  1995,  25:  2938 
    CrossrefGoogle Scholar
  • 2g Houllemare D. Outurquin F. Paulmier C. J. Chem. Soc., Perkin Trans. 1  1997,  1629 
    CrossrefGoogle Scholar
  • 2h Bieber LW. da Silva MF. da Costa RC. Silva LOS. Tetrahedron Lett.  1998,  39:  3655 
    CrossrefGoogle Scholar
  • 2i Kundu A. Prabhakar S. Vairamani M. Roy S. Organometallics  1999,  18:  2782 
    CrossrefGoogle Scholar
  • 2j Banerjee M. Roy S. Chem. Commun.  2003,  534 
    CrossrefGoogle Scholar
  • 2k Banerjee M. Roy S. Org. Lett.  2004,  6:  2137 
    CrossrefGoogle Scholar
  • For representative non-Barbier-type selective carbonyl allenylations and propargylations, see:
  • 3a Nokami J. Tamaoka T. Koguchi T. Okawara R. Chem. Lett.  1984,  1939 
    CrossrefGoogle Scholar
  • 3b Suzuki M. Morita Y. Noyori R. J. Org. Chem.  1990,  55:  441 
    CrossrefGoogle Scholar
  • 3c Brown HC. Khire UR. Narla G. Racherla US. J. Org. Chem.  1995,  60:  544 
    CrossrefGoogle Scholar
  • 3d Kobayashi S. Nishio K. J. Am. Chem. Soc.  1995,  117:  6392 
    CrossrefGoogle Scholar
  • 3e Marshall JA. Yu RH. Perkins JF. J. Org. Chem.  1995,  60:  5550 
    CrossrefGoogle Scholar
  • 3f Marshall JA. Grant CM. J. Org. Chem.  1999,  64:  8214 
    CrossrefGoogle Scholar
  • 3g Nakajima M. Saito M. Hashimoto S. Tetrahedron: Asymmetry  2002,  13:  2449 ; and references cited therein
    CrossrefGoogle Scholar
  • For the preparation of allenyltin and propargyltin compounds, see:
  • 4a Guillemin J.-C. Malagu K. Organometallics  1999,  18:  5259 
    CrossrefPubMedGoogle Scholar
  • 4b Kjellgren J. Sunden H. Szabo KJ. J. Am. Chem. Soc.  2005,  127:  1787 
    CrossrefPubMedGoogle Scholar
  • 5 Lin MJ. Loh TP. J. Am. Chem. Soc.  2003,  125:  13042 
    CrossrefPubMedGoogle Scholar
  • 6 Masuyama Y. Watabe A. Kurusu Y. Synlett  2003,  1713 
    Article in Thieme ConnectGoogle Scholar
  • 7a Masuyama Y. Ito A. Fukuzawa M. Terada K. Kurusu Y. Chem. Commun.  1998,  2025 
    CrossrefGoogle Scholar
  • 7b Masuyama Y. Watabe A. Ito A. Kurusu Y. Chem. Commun.  2000,  2009 
    CrossrefGoogle Scholar
  • 8 For carbonyl allylation with SnI4 and TBAI, see: Masuyama Y. Takeuchi K. Kurusu Y. Tetrahedron Lett.  2005,  46:  2861 
    CrossrefGoogle Scholar
  • 10a Since 1b caused no carbonyl propargylation, 3-methylpropargyltriiodotin would scarcely isomerize to 1-methylallenyltriiodotin on account of the steric hindrance of the methyl group. Thus, the bulkier trimethylsilyl group should give an unusual effect for the isomerization of A to C. It is presumed that the formation of a higher coordinated silicon intermediate causes regioselective ring-opening reactions of α-silylepoxides at the α-carbon near to the silyl group: Eisch JJ. Galle JE. J. Org. Chem.  1976,  41:  2615 
    CrossrefGoogle Scholar
  • 10b Soderquist JA. Santiago B. Tetrahedron Lett.  1989,  30:  5693 . Following the ring-opening reactions of α-silyl-epoxides, we propose stannylsilicate B as a plausible intermediate for the isomerization of A to C
    CrossrefGoogle Scholar
9

It was confirmed by 1H NMR analysis (JEOL Λ-500) that the reaction of 4 (0.03 mmol) with SnI2 (0.04 mmol) and NaI (0.04 mmol) in DMF-d 7 (0.5 mL) at 25 °C first produced propargyltin A, δ = 4.06 ppm (CH2, s), and then produced a small yield of allenyltin C, δ = 4.90 ppm (C = CH2, s).