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Synlett 2005(3): 406-410  
DOI: 10.1055/s-2004-837219
LETTER
© Georg Thieme Verlag Stuttgart · New York

Highly Regio- and Stereoselective Hydrostannylation of Propargyl Alcohols and Ethers Using Dibutylchlorostannane and Lithium Chloride

Katsukiyo Miura*, Di Wang, Akira Hosomi*
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, and CREST, Japan Science and ­Technology Corporation (JST), Tsukuba, Ibaraki 305-8571, Japan
Fax: +81(29)8536503; e-Mail: hosomi@chem.tsukuba.ac.jp;
Further Information

Publication History

Received 22 November 2004
Publication Date:
22 December 2004 (online)

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Abstract

In the presence of LiCl, dibutylchlorostannane (Bu2SnClH) reacted with γ-unsubstituted propargyl alcohols and ethers to give γ-stannylated allyl alcohols and ethers, respectively, with high regio- and stereoselectivity. These vinylstannane products could be successfully utilized for the Pd-catalyzed cross-coupling reaction.

Key words

alcohols - alkynes - cross-coupling - hydrostannations - radical reactions

    References

  • 1a Davies AG. Organotin Chemistry   Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 1b Kosugi M. Fugami K. In Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1:  Negishi E. Wiley; New York: 2002.  Chap. III.2.3. p.263 
    Google Scholar
  • 1c Mitchell TN. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  Chap. 4. p.167 
    Google Scholar
  • 1d Pereyre M. Quintard J.-P. Rahm A. Tin in Organic Synthesis   Butterworths; London: 1987. 
    Google Scholar
  • 1e Stille JK. Angew Chem., Int. Ed. Engl.  1986,  25:  508 
    Google Scholar
  • 2a Davies AG. In Comprehensive Organometallic Chemistry II   Vol. 2:  Abel EW. Stone FGA. Wilkinson G. Pergamon; Oxford, UK: 1995.  p.217 
    Google Scholar
  • 2b Kupchik EJ. In Organotin Compounds   Vol. 1:  Sawyer AK. Dekker; New York: 1971.  Chap. 2. p.7 
    Google Scholar
  • 3a Leusink AJ. Budding HA. J. Organomet. Chem.  1968,  11:  533 
    CrossrefGoogle Scholar
  • 3b Nozaki K. Oshima K. Utimoto K. J. Am. Chem. Soc.  1987,  109:  2547 
    CrossrefGoogle Scholar
  • 3c Mitchell TN. Amamria A. J. Organomet. Chem.  1983,  252:  47 
    CrossrefGoogle Scholar
  • 3d Nakamura E. Imanishi Y. Machii D. J. Org. Chem.  1994,  59:  8178 
    CrossrefGoogle Scholar
  • 4a Ichinose Y. Oda H. Oshima K. Utimoto K. Bull. Chem. Soc. Jpn.  1987,  60:  3468 
    CrossrefPubMedGoogle Scholar
  • 4b Zhang HX. Guibé F. Balavoine G. J. Org. Chem.  1990,  55:  1857 
    CrossrefPubMedGoogle Scholar
  • 4c Betzer J.-F. Delaloge F. Muller B. Pancrazi A. Prunet J. J. Org. Chem.  1997,  62:  7768 
    CrossrefPubMedGoogle Scholar
  • 4d Mitchell TN. Moschref S.-N. Synlett  1999,  1259 
    CrossrefPubMedGoogle Scholar
  • 4e Smith ND. Mancuso J. Lautens M. Chem. Rev.  2000,  100:  3257 ; and references therein
    CrossrefPubMedGoogle Scholar
  • 5 Asao N. Liu J.-X. Sudoh T. Yamamoto Y. J. Chem. Soc., Chem. Commun.  1995,  2405 
    CrossrefGoogle Scholar
  • 6 Shibata I. Suwa T. Ryu K. Baba A. J. Am. Chem. Soc.  2001,  123:  4101 
    CrossrefGoogle Scholar
  • 7 Miura K. Wang D. Matsumoto Y. Fujisawa N. Hosomi A. J. Org. Chem.  2003,  68:  8730 
    CrossrefGoogle Scholar
  • 8 For a related work by us, see: Miura K. Saito H. Uchinokura S. Hosomi A. Chem. Lett.  1999,  659 
    CrossrefGoogle Scholar
  • Quite recently, Mitchell et al. have reported results similar to those reported previously by us. See:
  • 9a Thiele CM. Mitchell TN. Eur. J. Org. Chem.  2004,  337 
    CrossrefGoogle Scholar
  • 9b Highly regio- and stereoselective hydrostannylation of γ-unsubstituted propargyl ethers with Bu2SnClH was also reported by them; however, the high regioselectivity could not be reproduced by our hands. See: Mitchell TN. Moschref S.-N. Chem. Commun.  1998,  1201 
    CrossrefGoogle Scholar
  • 11a Gallagher WP. Terstiege I. Maleczka RE. J. Am. Chem. Soc.  2001,  123:  3194 
    CrossrefGoogle Scholar
  • 11b Maleczka RE. Gallagher WP. Org. Lett.  2001,  3:  4173 
    CrossrefGoogle Scholar
  • 11c Maleczka RE. Gallagher WP. Terstiege I. J. Am. Chem. Soc.  2000,  122:  384 
    CrossrefGoogle Scholar
  • 11d Maleczka RE. Lavis JM. Clark DH. Gallagher WP. Org. Lett.  2000,  2:  3655 
    CrossrefGoogle Scholar
  • 12a Neumann WP. Pedain J. Tetrahedron Lett.  1964,  2461 
    CrossrefGoogle Scholar
  • 12b Davies AG. Kinart WJ. Osei-Kissi DK. J. Organomet. Chem.  1994,  474:  C11 
    CrossrefGoogle Scholar
  • γ-Substituted propargyl alcohols are known to undergo β-regioselective hydrostannylation with Bu3SnH in the presence of a radical initiator. See:
  • 14a Ensley HE. Buescher RR. Lee K. J. Org. Chem.  1982,  47:  404 
    Google Scholar
  • 14b Konoike T. Araki Y. Tetrahedron Lett.  1992,  33:  5093 
    Google Scholar
  • 15 The 119Sn signal of Bu2SnClH (8 mmol in 1 mL of THF-d 8) was reported to appear at δ = -18.3 ppm. See: Kawakami T. Sugimoto T. Shibata I. Baba A. Matsuda H. Sonoda N. J. Org. Chem.  1995,  60:  2677 
    CrossrefGoogle Scholar
  • Shibata and Baba et al. have reported that halide ions and HMPA easily complex Bu2SnXH (X = F, Cl, Br, I), and that the resulting 5-coordinate tin compounds can be successfully used as reducing and hydrostannylating agents. See ref. 6, ref.14, and the following references:
  • 16a Shibata I. Kato H. Kanazawa N. Yasuda M. Baba A. Synlett  2004,  137 
    CrossrefGoogle Scholar
  • 16b Shibata I. Baba A. Curr. Org. Chem.  2002,  6:  665 ; and references therein
    CrossrefGoogle Scholar
  • 17 Silverstein RM. Bassler GC. Morrill TC. Spectrometric Identification of Organic Compounds   5th ed.:  Wiley; New York: 1991. 
    Google Scholar
  • 19a Fugami K. Ohnuma S. Kameyama M. Saotome T. Kosugi M. Synlett  1999,  63 
    CrossrefGoogle Scholar
  • 19b Fouquet E. Pereyre M. Rodriguez AL. J. Org. Chem.  1997,  62:  5242 
    CrossrefGoogle Scholar
  • 20a Martinez AG. Barcina JO. de Fresno Cerezo A. Subramanian LR. Synlett  1994,  1047 
    CrossrefGoogle Scholar
  • 20b Vedejs E. Haight AR. Moss WO. J. Am. Chem. Soc.  1992,  114:  6556 
    CrossrefGoogle Scholar
  • 22 Espinet P. Echavarren AM. Angew. Chem. Int. Ed.  2004,  43:  4704 
    PubMedGoogle Scholar
10

For the Et3B-initiated reaction, see ref. [3b]

13

General Procedure for the Hydrostannylation of 1 with Bu 2 SnClH-LiCl Followed by Butylation:
Under N2, THF (1 mL) was added to a mixture of Bu2SnCl2 (83.5 mg, 0.275 mmol) and LiCl (21.2 mg, 0.500 mmol) at 0 °C. Bu2SnH2 (64.6 mg, 0.275 mmol) was added to the THF solution, and the mixture was stirred for 10 min at 0 °C. A propargyl alcohol 1 (0.500 mmol) was added to the resultant Bu2SnClH-LiCl solution. The mixture was warmed to r.t. and stirred for 3 h. The resultant mixture was cooled to 0 °C and treated with BuMgBr (1.00 M in Et2O, 1.30 mmol). After 20 min, the resultant mixture was poured into a 1:1 mixture of sat. aq NH4Cl and H2O. The extract with
t-BuOMe was dried over Na2SO4 and evaporated. Purification of the residual oil was performed by silica gel column chromatography (hexane-t-BuOMe 20:1).

18

The formation of Bu2SnClH from Bu2SnCl2 and Bu2SnH2 is known to be reversible. The initiation of the present homolytic hydrostannylation may be caused by electron transfer from Bu2SnH2 to Bu2SnCl2, which forms the anion radical of Bu2SnCl2. See ref. [12b]

21

General Procedure for the Subsequent Pd-Catalyzed Cross-Coupling:
PPh3, Pd2(dba)3·CHCl3, TBAF (1.0 M in THF, 1.5 mmol), and a haloarene (0.550 mmol) were added successively to the reaction mixture obtained by the hydrostannylation of 1a or 8c (0.500 mmol). After being stirred at 60 °C for a given time, the resultant mixture was cooled to r.t. and diluted with t-BuOMe (10 mL). After addition of DBU (0.5 mL), the mixture was stirred for 5-10 min, passed through a short silica gel column, and evaporated. Purification of the residual oil was performed by silica gel column chromatography.