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Synlett 2009(13): 2105-2108  
DOI: 10.1055/s-0029-1217701
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Chemoselective Isomerization of Secondary-Type Propargylic Alcohols to Propargylic/Allenic Bromides, and Brominated Dienes with Appel-Type Reaction Conditions

Norio Sakai*, Tsukasa Maruyama, Takeo Konakahara
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science (RIKADAI), Noda, Chiba 278-8510, Japan
Fax: +81(4)71239890; e-Mail: sakachem@rs.noda.tus.ac.jp;
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Publication History

Received 7 May 2009
Publication Date:
16 July 2009 (online)

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Abstract

Herein is described the chemoselective isomerization of secondary-type propargylic alcohols to allenic bromides, propargylic bromides and brominated dienes under Appel-type reaction conditions containing Ph3P, CBr4 and additives.

Key words

Appel reaction - propargylic alcohol - allene - diene - isomerization

    References and Notes

  • 1 Hoffmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 
    CrossrefPubMedGoogle Scholar
  • For selected recent books and reviews for allene chemistry, see:
  • 2a Krause N. Hashmi ASK. In Modern Allene Chemistry   Vol. 1:  Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 2b Krause N. Hashmi ASK. In Modern Allene Chemistry   Vol. 2:  Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 2c Kwong CK.-W. Fu MY. Lam CS.-L. Toy PH. Synthesis  2008,  2307 
    Google Scholar
  • 2d Ma S. Chem. Rev.  2005,  105:  2829 
    Google Scholar
  • 2e Miesch M. Synthesis  2004,  746 
    Google Scholar
  • 2f Krause N. Hoffmann-Röder A. Tetrahedron  2004,  60:  11671 
    Google Scholar
  • 2g Lu X. Zhang C. Xu Z. Acc. Chem. Res.  2001,  34:  535 
    Google Scholar
  • 3 Sakai N. Hirasawa M. Konakahara T. Tetrahedron Lett.  2005,  46:  6407 
    CrossrefGoogle Scholar
  • 4a Das B. Damodar K. Bhunia N. Shashikanth B. Tetrahedron Lett.  2009,  50:  2072 
    Google Scholar
  • 4b Das B. Kanth BS. Reddy KR. Satyalakshmi G. Kumar RA. Chem. Lett.  2008,  37:  512 
    Google Scholar
  • 5 Appel R. Angew. Chem., Int. Ed. Engl.  1975,  14:  801 
    CrossrefGoogle Scholar
  • 6a Alexakis A. Marek I. Mangeney P. Normant JF.
    J. Am. Chem. Soc.  1990,  112:  8042 
    Google Scholar
  • 6b Marek I. Mangeney P. Alexakis A. Normant JF. Tetrahedron Lett.  1986,  27:  5499 
    Google Scholar
  • 6c Rona P. Crabbe P. J. Am. Chem. Soc.  1969,  91:  3289 
    Google Scholar
  • 6d Rona P. Crabbe P. J. Am. Chem. Soc.  1968,  90:  4733 
    Google Scholar
  • 7a Keinan E. Bosch E. J. Org. Chem.  1986,  51:  4006 
    Google Scholar
  • 7b Elsevier CJ. Stehouwer PM. Westmijze H. Vermeer P. J. Org. Chem.  1983,  48:  1103 
    Google Scholar
  • 8a Moreau J.-L. Gaudemar M. J. Organomet. Chem.  1976,  108:  159 
    Google Scholar
  • 8b Alexakis A. Commercon A. Villiéras J. Normant JF. Tetrahedron Lett.  1976,  2313 
    Google Scholar
  • 9 Wenkert E. Leftin MH. Michelotti EL. J. Org. Chem.  1985,  50:  1122 
    CrossrefGoogle Scholar
  • 10a Riveiros R. Rodriguez D. Perez Sestelo J. Sarandeses LA. Org. Lett.  2006,  8:  1403 
    Google Scholar
  • 10b Yoshida M. Gotou T. Ihara M. Tetrahedron Lett.  2004,  45:  5573 
    Google Scholar
  • 10c Lee K. Seomoon D. Lee PH. Angew. Chem. Int. Ed.  2002,  41:  3901 
    Google Scholar
  • 10d Pasto DJ. Chou S.-K. Waterhouse A. Shults RH. Hennion GF. J. Org. Chem.  1978,  43:  1385 
    Google Scholar
  • 11a Sanz R. Miguel D. Martinez A. Alvarez-Gutierrez JM. Rodriguez F. Org. Lett.  2007,  9:  727 
    Google Scholar
  • 11b Huang W. Wang J. Shen Q. Zhou X. Tetrahedron  2007,  63:  11636 
    Google Scholar
  • 11c Ishikawa T. Aikawa T. Mori Y. Saito S. Org. Lett.  2003,  5:  51 
    Google Scholar
  • 11d Ishikawa T. Okano M. Aikawa T. Saito S. J. Org. Chem.  2001,  66:  4635 
    Google Scholar
  • 12a Myers AG. Zheng B. J. Am. Chem. Soc.  1996,  118:  4492 
    Google Scholar
  • 12b Corey EJ. Boaz NW. Tetrahedron Lett.  1984,  25:  3055 
    Google Scholar
  • 12c Parker KA. Petraitis JJ. Tetrahedron Lett.  1977,  4561 
    Google Scholar
  • 14a Guo C. Lu X. J. Chem. Soc., Perkin Trans. 1  1993,  1921 
    Google Scholar
  • 14b Trost BM. Kazmaier U. J. Am. Chem. Soc.  1992,  114:  7933 
    Google Scholar
  • 14c Trost BM. Schmidt T. J. Am. Chem. Soc.  1988,  110:  2301 
    Google Scholar
  • 14d Lu X. Ma D. Pure Appl. Chem.  1990,  62:  723 
    Google Scholar
  • 15 When the same reaction was conducted with CCl4 instead of CBr4, the corresponding chlorinated allene derivative was obtained in 40% yield. For a selected paper on the SN2-type chlorination of a primary alcohol using CCl4 and PPh3, see: Lee JB. Downie IM. Tetrahedron  1967,  23:  359 
    CrossrefGoogle Scholar
  • 18a Slagle JD. Huang TTS. Franzus B. J. Org. Chem.  1981,  46:  3526 
    Google Scholar
  • 18b Jones LA. Sumner CE. Franzus B. Huang TTS. Snyder EI. J. Org. Chem.  1978,  43:  2821 
    Google Scholar
13

General Procedure for the Synthesis of Allene Derivatives 2: CBr4 (331 mg, 1.0 mmol), Ph3P (262 mg, 1.0 mmol), propargylic alcohol 1 (0.50 mmol), i-Pr2NEt (129 mg, 1.0 mmol), P(n-Bu)3 (10 mg, 0.05 mmol), and a freshly distilled toluene (1 mL) were successively added into a screw-capped vial, and the vial was sealed with a cap containing a PTFE septum. The reaction mixture was stirred at 100 ˚C, and monitored by TLC until the propargylic alcohol 1 was consumed. To quench the reaction, H2O (2 mL) was added to the mixture. The mixture was extracted with CH2Cl2 (3 ×), and the combined organic extracts were dried over Na2SO4, filtered, and then evaporated under reduced pressure. The crude product was purified by silica gel chromatography(hexane) to produce the allene derivative 2, and if necessary, was further purified by a recycling preparative HPLC equipped with a GPC column (chloroform as an eluent). Spectral data for selected compound: 1-(3-Bromo-1,2-nonadien-1-yl)benzene (2a): pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 0.86 (t, 3 H, J = 7.2 Hz), 1.24-1.38 (m, 6 H), 1.50 (quint, 2 H, J = 7.2 Hz), 2.52 (td, 2 H, J = 7.2, 3.0 Hz), 6.19 (t, 1 H, J = 3.0 Hz), 7.23-7.27 (m, 1 H), 7.32-7.33 (m, 4 H). ¹³C NMR (75 MHz, CDCl3): δ = 13.9, 22.5, 27.9, 28.2, 31.4, 38.0, 96.1, 100.3, 127.7, 128.1, 128.7, 133.0, 199.8. MS (FAB): m/z (%) = 281 (100) [M+], 279 (40) [M+]. HRMS (FAB): m/z calcd for C15H20Br: 279.0748; found: 279.0726.

16

General Procedure for the Synthesis of Diene Derivatives 3: The same procedure as above without i-Pr2NEt gave the diene derivative 3. However, formation of a quite small amount of the (1Z,3E)-diene along with the (1E,3E)-diene separable by column chromatography was observed by NMR. Spectral data for selected compound: [(1E,3E)-3-Bromo-1,3-nonadien-1-yl]benzene (3a): pale brown oil. ¹H NMR (300 MHz, CDCl3): δ = 0.88 (t, 3 H, J = 7.2 Hz), 1.27 (m, 3 H), 1.35 (m, 1 H), 1.47 (m, 2 H), 2.35 (q, 2 H, J = 7.2 Hz), 6.08 (t, 1 H, J = 7.2 Hz), 6.73 (d, 1 H, J = 15.0 Hz), 6.89 (d, 1 H, J = 15.0 Hz), 7.23 (m, 1 H), 7.30 (m, 2 H), 7.42 (m, 2 H). ¹³C NMR (75 MHz, CDCl3): δ = 13.9, 22.4, 28.1, 31.4, 31.7, 126.7, 126.9, 127.7, 127.9, 128.6, 128.7, 132.1, 135.3. MS (EI): m/z = 279 [M+]. HRMS (FAB): m/z calcd for C15H20Br: 279.0748; found: 279.0728. Stereochemistry (1E,3E) of the isolated compound was determined by
the chemical shift and coupling constant of the related compound. Specific peaks derived from (1Z,3E)-diene 3a were observed by ¹H NMR. ¹H NMR: δ = 5.87 (t, 1 H, J = 7.2 Hz), 6.76 (d, 2 H, J = 15.0 Hz), 6.94 (d, 1 H, J = 15.0 Hz). Other peaks overlapped with those of the (1E,3E)-diene.

17

We have no clear cause for the low yield of diene derivative 3; however, formation of several complex products, which were probably derived from the starting propargylic alcohol, was observed by an NMR measurement.