Synthesis 2011(15): 2383-2386  
DOI: 10.1055/s-0030-1260074
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Fluorohydrins through Electrophilic Fluorination of Allyl Silanes

Weibo Wang, Bo Xu*, Gerald B. Hammond*
Department of Chemistry, University of Louisville, Louisville, KY 40292, USA
Fax: +1(502)8523899; e-Mail: bo.xu@louisville.edu; e-Mail: gb.hammond@louisville.edu;
Further Information

Publication History

Received 29 April 2011
Publication Date:
17 June 2011 (eFirst)

Abstract

A convenient method for the efficient and regioselective monofluorination of allyl silanes to afford 1-fluoro-3-silyl-2-ols in 43-62% yields via fluorohydroxylation, using Selectfluor as the eletrophilic fluorination reagent has been developed. The regioselectivity can be rationalized by considering the stabilization of the β-carbocation intermediate by the silyl group.

    References

  • 1a Chambers RD. Fluorine in organic chemistry   Blackwell Publishing Ltd./CRC Press; Boca Raton: 2004. 
  • 1b Hiyama T. Organofluorine compounds, chemistry and applications   Springer-Verlag; Berlin: 2000. 
  • 1c Kirsch P. Modern fluoroorganic chemistry   Wiley-VCH; Weinheim: 2004. 
  • 1d Muller K. Faeh C. Diederich F. Science  2007,  317:  1881 
  • 1e Schlosser M. Angew. Chem. Int. Ed.  1998,  37:  1496 
  • 1f Soloshonok VA. Fluorine-containing synthons, ACS Symposium Series 911   Oxford University Press; Washington DC: 2005. 
  • 1g Uneyama K. Organofluorine Chemistry   Blackwell Publishing; Oxford: 2006. 
  • 2a Camps F. Fabrias G. Guerrero A. Tetrahedron  1986,  42:  3623 
  • 2b Fox DT. Poulter CD. J. Org. Chem.  2005,  70:  1978 
  • 2c Jie MSFLK. Lau MML. Lam CNW. Alam MS. Metzger JO. Biermann U. Chem. Phys. Lipids  2003,  125:  93 
  • 2d Kim HO. Lim MH. Park JG. Moon HR. Jacobson KA. Kim H.-D. Chun MW. Jeong LS. Nucleosides, Nucleotides Nucleic Acids  2003,  22:  923 
  • 2e Lan Y. Hammond GB. J. Org. Chem.  2000,  65:  4217 
  • 2f Lan Y. Hammond GB. Org. Lett.  2002,  4:  2437 
  • 2g Lim MH. Kim HO. Moon HR. Lee SJ. Chun MW. Gao Z.-G. Melman N. Jacobson KA. Kim JH. Jeong LS. Bioorg. Med. Chem. Lett.  2003,  13:  817 
  • 2h Mastihubova M. Biely P. Tetrahedron Lett.  2001,  42:  9065 
  • 2i Runge M. Haufe G. J. Org. Chem.  2000,  65:  8737 
  • 3a Akiyama Y. Fukuhara T. Hara S. Synlett  2003,  1530 
  • 3b Bruns S. Haufe G. J. Fluorine Chem.  2000,  104:  247 
  • 3c Islas-Gonzalez G. Puigjaner C. Vidal-Ferran A. Moyano A. Riera A. Pericas MA. Tetrahedron Lett.  2004,  45:  6337 
  • 3d Mikami K. Ohba S. Ohmura H.
    J. Organomet. Chem.  2002,  662:  77 
  • 3e Nicoletti M. O’Hagan D. Slawin AMZ. J. Am. Chem. Soc.  2005,  127:  482 
  • 3f Schaus SE. Brandes BD. Larrow JF. Tokunaga M. Hansen KB. Gould AE. Furrow ME. Jacobsen EN. J. Am. Chem. Soc.  2002,  124:  1307 
  • 3g Yoshino H. Nomura K. Matsubara S. Oshima K. Matsumoto K. Hagiwara R. Ito Y. J. Fluorine Chem.  2004,  125:  1127 
  • 4 Xu B. Hammond GB. J. Org. Chem.  2006,  71:  3518 
  • 5a Schueler M. Speciality Chemicals Magazine  2006,  26:  20 
  • 5b Nyffeler PT. Duron SG. Burkart MD. Vincent SP. Wong C.-H. Angew. Chem. Int. Ed.  2005,  44:  192 
  • 6 Zhou C. Li J. Lu B. Fu C. Ma S. Org. Lett.  2008,  10:  581 
  • 7 Wang W. Jasinski J. Hammond GB. Xu B. Angew. Chem. Int. Ed.  2010,  49:  7247 
  • 8 Wilkinson SC. Lozano O. Schuler M. Pacheco MC. Salmon R. Gouverneur V. Angew. Chem. Int. Ed.  2009,  48:  7083 
  • 9a Tredwell M. Gouverneur V. Org. Biomol. Chem.  2006,  4:  26 
  • 9b Pacheco MC. Gouverneur V. Org. Lett.  2005,  7:  1267 
  • 9c Greedy B. Paris J.-M. Vidal T. Gouverneur V. Angew. Chem. Int. Ed.  2003,  42:  3291 
  • 9d Sawicki M. Kwok A. Tredwell M. Gouverneur V. Beilstein J. Org. Chem.  2007,  3:  34 
  • 9e Carroll L. McCullough S. Rees T. Claridge TDW. Gouverneur V. Org. Biomol. Chem.  2008,  6:  1731 
  • 9f Carroll L. Pacheco MC. Garcia L. Gouverneur V. Chem. Commun.  2006,  4113 
  • 10 Olah GA. Prakash GKS. Carbocation chemistry   Wiley-Interscience; Hoboken NJ: 2004.