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Synlett 2005(14): 2251-2253  
DOI: 10.1055/s-2005-872255
LETTER
© Georg Thieme Verlag Stuttgart · New York

Iridium-Catalyzed Carbonyl Allylations by Allylic Alcohols with Tin(II) Chloride

Yoshiro Masuyama*, Toshiya Chiyo, 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 21 June 2005
Publication Date:
29 July 2005 (online)

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Abstract

Iridium complex [IrCl(cod)]2 can function as a catalyst for the allylation of aldehydes and ketones by allylic alcohols upon addition of an equimolar amount of SnCl2 in THF-H2O; the reaction is carried out between room temperature and 50 °C to give the corresponding homoallylic alcohols.

Key words

nucleophilic addition - carbonyl allylation - π-allyliridium - tin(II) chloride - allylic alcohols

    References

  • 1 Masuyama Y. Kaneko Y. Kurusu Y. Tetrahedron Lett.  2004,  45:  8969 
    CrossrefGoogle Scholar
  • For reviews containing carbonyl allylations by allylic alcohols via umpolung of π-allylpalladium, see:
  • 2a Masuyama Y. J. Synth. Org. Chem., Jpn.  1992,  50:  202 
    Google Scholar
  • 2b Masuyama Y. In Advances in Metal-Organic Chemistry   Vol. 3:  Liebeskind LS. JAI Press; Greenwich CT: 1994.  p.255-303  
    Google Scholar
  • 2c Tamaru Y. In Perspectives in Organopalladium Chemistry for the XXI Century   Tsuji J. Elsevier Science; Switzerland: 1999.  p.215-231  
    Google Scholar
  • 2d Tamaru Y. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002.  p.1917-1953  
    Google Scholar
  • 3 For the palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl2, see: Takahara JP. Masuyama Y. Kurusu Y. J. Am. Chem. Soc.  1992,  114:  2577 
    Google Scholar
  • Palladium-catalyzed carbonyl allylations need over two equivalents of reducing agent for one equivalent of allylic alcohol and/or aldehyde:
  • 4a For triethylborane, see: Kimura M. Tomizawa T. Horino Y. Tanaka S. Tamaru Y. Tetrahedron Lett.  2000,  41:  3627 
    CrossrefGoogle Scholar
  • 4b For indium iodide, see: Araki S. Kamei T. Hirashita T. Yamamura H. Kawai M. Org. Lett.  2000,  2:  847 
    CrossrefGoogle Scholar
  • 4c For diethylzinc, see: Kimura M. Shimizu M. Tanaka S. Tamaru Y. Tetrahedron  2005,  61:  3709 
    CrossrefGoogle Scholar
  • 5 For nickel-catalyzed carbonyl allylation with over two equivalents of indium iodide and one equivalent of aldehyde, see: Hirashita T. Kambe S. Tsuji H. Omori H. Araki S. J. Org. Chem.  2004,  69:  5054 
    CrossrefPubMedGoogle Scholar
  • 6 Takeuchi R. Synlett  2002,  1954 ; and references cited therein
    Article in Thieme ConnectGoogle Scholar
  • The structures and/or ratios were confirmed by comparison of the IR and 1H NMR spectra with those of authentic samples, see:
  • 8a

    ref. 3
    CrossrefGoogle Scholar
  • 8b Ito A. Kishida M. Kurusu Y. Masuyama Y. J. Org. Chem.  2000,  65:  494 
    CrossrefGoogle Scholar
  • Since the reactivity of cyclohexanecarboxaldehyde is low, initially produced 5b may react with excess cyclohexanecarboxaldehyde and isomerize to sterically unhindered and thermodynamically stable 5a via a homoallyloxycarbenium ion intermediate:
  • 9a Nokami J. Ohga M. Nakamoto H. Matsubara T. Hussain I. Kataoka K. J. Am. Chem. Soc.  2001,  123:  9168 
    CrossrefPubMedGoogle Scholar
  • 9b

    Ref. 1.
    CrossrefPubMedGoogle Scholar
7

A typical procedure is as follows: To a solution of 1 (0.087 g, 1.5 mmol), benzaldehyde (0.11 g, 1.0 mmol), and SnCl2 (0.28 g, 1.5 mmol) in THF (2 mL) and H2O (0.1 mL) was added [IrCl(cod)]2 (0.013 g, 0.02 mmol), and the solution was stirred at r.t. for 20 h. The solution was diluted with Et2O-CH2Cl2 (2:1; 120 mL), washed with aq 10% HCl solution (20 mL), aq NaHCO3 solution (20 mL), H2O (20 mL), and brine (20 mL). The extracts were dried over anhyd MgSO4. After evaporation of the solvent, column chromatography (silica gel; hexane-EtOAc, 7:1), and then HPLC (Japan Analytical Industry Co. Ltd., LC-908, JAIGEL-2H; CHCl3) afforded 0.13 g (87%) of 1-phenyl-3-buten-1-ol as a colorless oil.

10

1H NMR (500 MHz): δ = 3.93 (d, J = 6 Hz, 2 H), 5.09 (d, J = 10 Hz, 1 H), 5.23 (d, J = 17 Hz, 1 H), 5.83-5.91 (m, 1 H); 13C NMR (125 MHz): δ = 71.5, 116.0, 136.1.