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Synlett 2011(18): 2705-2708  
DOI: 10.1055/s-0031-1289535
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

TiCl4-Promoted Mukaiyama Aldol Reaction of Fluorinated Silyl Enolates for the Construction of a Quaternary Carbon Center

Wengui Wang, Qing-Yun Chen, Yong Guo*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: yguo@sioc.ac.cn;
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Publication History

Received 10 July 2011
Publication Date:
19 October 2011 (online)

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Abstract

A method for the preparation of α-fluoro-β-hydroxy­phenones from Mukaiyama aldol reactions of various aldehydes and fluorinated silyl enolates was reported. The reaction was promoted by TiCl4 and afforded the desired products in good to excellent yields. The relative stereochemistry of the products was determined by X-ray analysis of single crystals of syn-2-fluoro-3-hydroxy-2-methyl-1,3-diphenylpropan-1-one and anti-2-fluoro-3-hydroxy-2,4,4-trimethyl-1-phenylpentan-1-one.

Key words

aldol reaction - Lewis acids - fluorine - enols - aldehydes

    References and Notes

  • 1a Fluorine in Medicinal Chemistry and Chemical Biology   Ojima I. Wiley; Chichester: 2009. 
    Google Scholar
  • 1b Bégué J.-P. Bonnet-Delphon D. Bioorganic and Medicinal Chemistry of Fluorine   Wiley; Hoboken: 2008. 
    Google Scholar
  • 1c Uneyama K. Organofluorine Chemistry   Blackwell; Oxford: 2006. 
    Google Scholar
  • 1d Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications   Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 1e Chambers RD. Fluorine in Organic Chemistry   Blackwell; Oxford: 2004. 
    Google Scholar
  • 1f Organofluorine Compounds: Chemistry and Applications   Hiyama T. Springer; New York: 2000. 
    Google Scholar
  • For reviews, see:
  • 2a O’Hagan D. Chem. Soc. Rev.  2008,  37:  308 
    Google Scholar
  • 2b Müller K. Faeh C. Diederich F. Science  2007,  317:  1881 
    Google Scholar
  • 2c Mikami K. Itoh Y. Yamanaka M. Chem. Rev.  2004,  104:  1 
    Google Scholar
  • 2d Purser S. Moore PR. Swallow S. Gouverneur V. Chem. Soc. Rev.  2008,  37:  320 
    Google Scholar
  • 3 Thayer AM. Chem. Eng. News  2006,  84:  15 
    Google Scholar
  • 4 O’Hagan D. J. Fluorine Chem.  2010,  131:  1071 
    Google Scholar
  • 5a Davis FA. Kasu PVN. Org. Prep. Proced. Int.  1999,  31:  125 
    Google Scholar
  • 5b Cahard D. Xu X. Couve-Bonnaire S. Pannecoucke X. Chem. Soc. Rev.  2010,  39:  558 
    Google Scholar
  • 5c Lectard S. Hamashima Y. Sodeoka M. Adv. Synth. Catal.  2010,  352:  2708 
    Google Scholar
  • 5d Ma J.-A. Cahard D. Chem. Rev.  2008,  108:  PR1 
    Google Scholar
  • 5e Brunet VA. O’Hagan D. Angew. Chem. Int. Ed.  2008,  47:  1179 
    Google Scholar
  • 5f Shibata N. Ishimaru T. Nakamura S. Toru T. J. Fluorine Chem.  2007,  128:  469 
    Google Scholar
  • 5g Prakash GKS. Beier P. Angew. Chem. Int. Ed.  2006,  45:  2172 
    Google Scholar
  • 5h Pihko PM. Angew. Chem. Int. Ed.  2006,  45:  544 
    Google Scholar
  • 5i Bobbio C. Gouverneur V. Org. Biomol. Chem.  2006,  4:  2065 
    Google Scholar
  • 5j Hamashima Y. Sodeoka M. Synlett  2006,  1467 
    Google Scholar
  • 5k Mikami K. Itoh Y. Yamanaka M. Chem. Rev.  2004,  104:  1 
    Google Scholar
  • 6a Smith AMR. Hii KKM. Chem. Rev.  2011,  111:  1637 
    Google Scholar
  • 6b Shibatomi K. Synthesis  2010,  2679 
    Google Scholar
  • 6c Bella M. Gasperi T. Synthesis  2009,  1583 
    Google Scholar
  • 6d Ueda M. Kano T. Maruoka K. Org. Biomol. Chem.  2009,  7:  2005 
    Google Scholar
  • 6e Cozzi PG. Hilgraf R. Zimmermann N. Eur. J. Org. Chem.  2007,  5969 
    Google Scholar
  • 6f Marigo M. Jørgensen KA. Chem. Commun.  2006,  2001 
    Google Scholar
  • 6g Oestreich M. Angew. Chem. Int. Ed.  2005,  44:  2324 
    Google Scholar
  • 6h France S. Weatherwax A. Lectka T. Eur. J. Org. Chem.  2005,  475 
    Google Scholar
  • 6i Ibrahim H. Togni A. Chem. Commun.  2004,  1147 
    Google Scholar
  • 7a Shibatomi K. Futatsugi K. Kobayashi F. Iwasa S. Yamamoto H. J. Am. Chem. Soc.  2010,  132:  5625 
    Google Scholar
  • 7b Shibatomi K. Yamamoto H. Angew. Chem. Int. Ed.  2008,  47:  5796 
    Google Scholar
  • 7c Arai S. Oku M. Ishida T. Shioiri T. Tetrahedron Lett.  1999,  40:  6785 
    Google Scholar
  • 7d Nakamura M. Hajra A. Endo K. Nakamura E. Angew. Chem. Int. Ed.  2005,  44:  7248 
    Google Scholar
  • 7e Burger EC. Barron BR. Tunge JA. Synlett  2006,  2824 
    Google Scholar
  • 7f Bélanger . Cantin K. Messe O. Tremblay M. Paquin J.-F. J. Am. Chem. Soc.  2007,  129:  1034 
    Google Scholar
  • 7g Bélanger E. Houzé C. Guimond N. Cantin K. Paquin J.-F. Chem. Commun.  2008,  3251 
    Google Scholar
  • 7h Bélanger E. Pouliot M.-F. Paquin J.-F. Org. Lett.  2009,  11:  2201 
    Google Scholar
  • 7i Guo Y. Twamley B. Shreeve JM. Org. Biomol. Chem.  2009,  7:  1716 
    Google Scholar
  • 7j Guo Y. Tao G.-H. Blumenfeld A. Shreeve JM. Organometallics  2010,  29:  1818 
    Google Scholar
  • 7k Shibatomi K. Narayama A. Soga Y. Muto T. Iwasa S. Org. Lett.  2011,  13:  2944 
    Google Scholar
  • 7l Kang SH. Kim DY. Adv. Synth. Catal.  2010,  352:  2783 
    Google Scholar
  • 8 For reviews, see: Brownbridge P. Synthesis  1983,  1 
    Google Scholar
  • For reviews, see:
  • 9a Gröger H. Vogl EM. Shibasaki M. Chem. Eur. J.  1998,  4:  1137 
    Google Scholar
  • 9b Denmark SE. Stavenger RA. Acc. Chem. Res.  2000,  33:  432 
    Google Scholar
  • 9c Schetter B. Mahrwald R. Angew. Chem. Int. Ed.  2006,  45:  7506 
    Google Scholar
  • 9d Geary LM. Hultin PG. Tetrahedron: Asymmetry  2009,  20:  131 
    Google Scholar
  • 10 Kobayashi S. Fujishita Y. Mukaiyama T. Chem. Lett.  1990,  1455 
    Google Scholar
  • 11a Palomo C. Oiarbide M. García JM. Chem. Eur. J.  2002,  8:  36 
    Google Scholar
  • 11b Schetter B. Mahrwald R. Angew. Chem. Int. Ed.  2006,  45:  7506 
    Google Scholar
  • 11c Adachi S. Harada T. Eur. J. Org. Chem.  2009,  3661 
    Google Scholar
  • 11d Geary LM. Hultin PG. Tetrahedron: Asymmetry  2009,  20:  131 
    Google Scholar
  • 12a Kobayashi S. Nagayama S. Busujima T. Tetrahedron  1999,  55:  8739 
    Google Scholar
  • 12b Mei Y. Dissanayake P. Allen MJ. J. Am. Chem. Soc.  2010,  132:  12871 
    Google Scholar
  • 12c Curti C. Battistini L. Zanardi F. Rassu G. Zambrano V. Pinna L. Casiraghi G. J. Org. Chem.  2010,  75:  8681 
    Google Scholar
  • 13 Alam J. Keller TH. Loh T.-P. J. Am. Chem. Soc.  2010,  132:  9546 
    Google Scholar
  • 14a Huang X.-T. Chen Q.-Y. J. Org. Chem.  2002,  67:  3231 
    Google Scholar
  • 14b Zhou D.-Y. Chen Q.-Y. Chin. J. Chem.  2004,  22:  953 
    Google Scholar
  • 14c Iseki K. Kuroki Y. Kobayashi Y. Tetrahedron Lett.  1997,  38:  7209 
    Google Scholar
  • 14d Iseki K. Kuroki Y. Kobayashi Y. Synlett  1998,  437 
    Google Scholar
  • 14e Iseki K. Kuroki Y. Kobayashi Y. Tetrahedron  1999,  55:  2225 
    Google Scholar
  • 15 For a review, see: Mukaiyama T. Angew. Chem., Int. Ed. Engl.  1977,  16:  817 
    Google Scholar
  • 18a Denmark SE. Stavenger RA. Wong K.-T. Su X.
    J. Am. Chem. Soc.  1999,  121:  4982 
    Google Scholar
  • 18b

    Cambridge Structural Database.

16

See Supporting Information for details. The complete crystallographic data can be obtained under the deposition numbers CCDC 833428 from the Cambridge Crystallo-graphic Data Centre.

17

See Supporting Information for details. The complete crystallographic data can be obtained under the deposition numbers CCDC 833429 from the Cambridge Crystallo-graphic Data Centre.