PDF herunterladen
Synlett 2011(14): 2039-2042  
DOI: 10.1055/s-0030-1261173
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Me3Ga-Mediated Addition of Acetylenes to α-Keto Esters: A New Method for the Synthesis of α-Hydroxy Esters

Honglai Jianga, Aijun Lina, Hao Penga, Yuhua Zhua, Yi Pana, Chengjian Zhu*a,b, Yixiang Cheng*a
a School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. of China
Fax: +86(25)83594886; e-Mail: cjzhu@nju.edu.cn;
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
Weitere Informationen

Publikationsverlauf

Received 24 April 2011
Publikationsdatum:
10. August 2011 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Trimethylgallium reagent was found to promote the addition of acetylenes to various α-keto esters. This reaction was efficiently carried out in anhydrous hexane at room temperature under mild conditions, and the corresponding α-hydroxy esters were obtained in good to excellent yields.

Key words

trimethylgallium - alkynylation - α-keto ester - α-hydroxy ester - acetylene

    References and Notes

  • 1a Comins DL. Hong H. Saha JK. Jianhua G. J. Org. Chem.  1994,  59:  5120 
    Google Scholar
  • 1b Senanayake CH. Fang QK. Grover P. Bakale RB. Vandenbossche CP. Wald SA. Tetrahedron Lett.  1999,  40:  819 
    Google Scholar
  • 1c Shilova EV. Pharm. Chem. J.  2000,  34:  419 
    Google Scholar
  • 1d Skaddan MB. Kilbourn MR. Snyder SE. Sherman PS. Desmond TJ. Frey KA. J. Med. Chem.  2000,  43:  4552 
    Google Scholar
  • 1e Okumura Y. Ando A. William Stevens R. Shimizu M. Tetrahedron  2002,  58:  8729 
    Google Scholar
  • 1f Sergeeva NN. Golubev AS. Henning L. Burger K. Synthesis  2003,  915 
    Google Scholar
  • 1g Zha C. Brown GB. Brouillette WJ. J. Med. Chem.  2004,  47:  6519 
    Google Scholar
  • 1h Tchilibon S. Zhang J. Yang Q.-F. Eidelman O. Kim H. Caohuy H. Jacobson KA. Pollard BS. Pollard HB. Biochem. Pharmacol.  2005,  70:  381 
    Google Scholar
  • 1i Tokuda O. Kano T. Gao W.-G. Ikemoto T. Org. Lett.  2005,  7:  5103 
    Google Scholar
  • 1j Tangirala RS. Antony S. Agama K. Pommier Y. Anderson BD. Bevins R. Curran DP. Bioorg. Med. Chem.  2006,  14:  6202 
    Google Scholar
  • 1k Xu Y. Etgen GJ. Broderick CL. Canada E. Gonzalez I. Lamar J. Montrose-Rafizadeh C. Oldham BA. Osborne JJ. Xie C. Shi Q. Winneroski LL. York J. Yumibe N. Zink R. Mantlo N. J. Med. Chem.  2006,  49:  5649 
    Google Scholar
  • 1l Jiménez-Teja D. Daoubi M. Collado IG. Hernández-Galán R. Tetrahedron  2009,  65:  3392 
    Google Scholar
  • 1m Nicolaou KC. Kang Q. Wu TR. Lim CS. Chen David K. J. Am. Chem. Soc.  2010,  132:  7540 
    Google Scholar
  • 2a DiMauro EF. Kozlowski MC. Org. Lett.  2002,  4:  3781 
    Google Scholar
  • 2b DiMauro EF. Kozlowski MC. J. Am. Chem. Soc.  2002,  124:  12668 
    Google Scholar
  • 2c Funabashi K. Jachmann M. Kanai M. Shibasaki M. Angew. Chem. Int. Ed.  2003,  42:  5489 
    Google Scholar
  • 2d Wieland LC. Deng H. Snapper ML. Hoveyda H. J. Am. Chem. Soc.  2005,  127:  15453 
    Google Scholar
  • 2e Fennie MW. DiMauro EF. O’Brien EM. Annamalai V. Kozlowski MC. Tetrahedron  2005,  61:  6249 
    Google Scholar
  • 2f Blay G. Fernández I. Marco-Aleixandre A. Pedro JR. Org. Lett.  2006,  8:  1287 
    Google Scholar
  • 2g Blay G. Fernández I. Marco-Aleixandre A. Pedro JR. Synthesis  2007,  3754 
    Google Scholar
  • 2h Wu HL. Wu PY. Shen YY. Uang BJ. J. Org. Chem.  2008,  73:  6445 
    Google Scholar
  • 2i Zheng B. Hou SC. Li ZY. Guo HC. Zhong JC. Wang M. Tetrahedron: Asymmetry  2009,  20:  2125 
    Google Scholar
  • 3 Hatano M. Ito O. Suzuki S. Ishihara K. Chem. Commun.  2010,  46:  2674 
    CrossrefGoogle Scholar
  • 4a Jiang B. Chen ZL. Tang XX. Org. Lett.  2002,  4:  3451 
    Google Scholar
  • 4b Cozzi PG. Rudolph J. Bolm C. Norrby P.-O. Tomasini C. J. Org. Chem.  2005,  70:  5733 
    Google Scholar
  • 5a Ooi T. Morikawa J. Ichikawa H. Maruoka K. Tetrahedron Lett.  1999,  40:  5881 
    Google Scholar
  • 5b Utimoto K. Lambert C. Fukuda Y. Shiragami H. Nozaki H. Tetrahedron Lett.  1984,  25:  5423 
    Google Scholar
  • 6a Zhu CJ. Yuan F. Gu WJ. Pan Y. Chem. Commun.  2003,  692 
    Google Scholar
  • 6b Yuan F. Zhu CJ. Sun JT. Liu YJ. Pan Y. J. Organomet. Chem.  2003,  682:  102 
    Google Scholar
  • 7a Nishimura Y. Miyake Y. Amemiya R. Yamaguchi M. Org. Lett.  2006,  8:  5077 
    Google Scholar
  • 7b Nishimura Y. Amemiya R. Yamaguchi M. Tetrahedron Lett.  2006,  47:  1839 
    Google Scholar
  • 8 Han Y. Fang L. Tao WT. Huang YZ. Tetrahedron Lett.  1995,  36:  1287 
    CrossrefGoogle Scholar
  • 9a Dai ZY. Zhu CJ. Yang MH. Zheng YF. Pan Y. Tetrahedron: Asymmetry  2005,  16:  605 
    Google Scholar
  • 9b Jia XF. Yang HW. Fang L. Zhu CJ. Tetrahedron Lett.  2008,  49:  1370 
    Google Scholar
  • 9c Jia XF. Fang L. Lin AJ. Pan Y. Zhu CJ. Synlett  2009,  495 
    Google Scholar
  • 11 Dahmen S. Org. Lett.  2004,  6:  2113 
    CrossrefGoogle Scholar
  • 12a Uhl W. Breher F. Haddadpour S. Koch R. Matar M. Z. Anorg. Allg. Chem.  2004,  630:  1839 
    Google Scholar
  • 12b Chmiel J. Neumann B. Stammler H.-G. Mitzel NW. Chem. Eur. J.  2010,  16:  1 
    Google Scholar
10

General Experimental Procedure
In a 20 mL Schlenk reaction tube, 1 M solution of Me3Ga (0.15 mL, 0.15 mmol, 1 M in toluene) and 4-methoxy-phenylacetylene (20 mg, 0.15 mmol) were dissolved in anhyd hexane (1 mL) and stirred for 1 h at r.t. under an nitrogen atmosphere. Then the mixture was cooled to 0 ˚C and methyl benzoylformate (0.1 mmol) was added, and stirred at r.t. for indicated time in Table  [²] , then sat. NH4Cl (1 mL) was added to quench the reaction. The aqueous layer was separated and further extracted with EtOAc, the organic layers were combined and dried. Evaporation of the solvent gave the crude product, which was further purified by preparative TLC (PE-EtOAc = 10:1) to give corresponding α-hydroxy esters.