Synthesis 2012(6): 903-908  
DOI: 10.1055/s-0031-1289702
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Exploiting the Addition of Trimethyl(trifluoromethyl)silane to Functionalized N-Benzylimines for the Preparation of Two Novel x-Trifluoromethyl x-Amino Acids

Anton N. Tkachenkoa,b, Dmytro S. Radchenkoa,b, Pavel K. Mykhailiuk*a,b, Oleg V. Shishkinc,d, Andrei A. Tolmacheva,b, Igor V. Komarova,b
a Enamine Ltd., Vul. Oleksandra Matrosova 23, 01103 Kyiv, Ukraine
b Department of Chemistry, Kyiv National Taras Shevchenko University, Vul. Volodymyrska 64, 01033 Kyiv, Ukraine
c SSI, Institute for Single Crystals, National Academy of Science of Ukraine, 60 Lenina Ave., 61001 Kharkiv, Ukraine
d Department of Inorganic Chemistry V. N., Karazin Kharkiv National University, Vul. Svobody 4, 61022 Kharkiv, Ukraine
e-Mail: Pavel.Mykhailiuk@gmail.com;
Further Information

Publication History

Received 30 November 2011
Publication Date:
13 February 2012 (eFirst)

Abstract

Straightforward gram-scale syntheses of a novel γ-tri­fluoromethyl γ-amino acid and a novel ε-trifluoromethyl-ε-amino acid are described. The key step in both syntheses is an acid-catalyzed nucleophilic trifluoromethylation of a cyclic N-benzylimine possessing an ester group by using the Ruppert--Prakash reagent [trimethyl(trifluoromethyl)silane]. The strategy provides a potentially general approach for the synthesis of x-trifluoromethyl x-amino acids.

    References

  • For reviews on bioisosteric replacements, see:
  • 1a Meanwell NA. J. Med. Chem.  2011,  54:  2529 
  • 1b Patani GA. LaVoie EJ. Chem. Rev.  1996,  96:  3147 
  • 1c Venkatesan N. Kim BH. Curr. Med. Chem.  2002,  9:  2243 
  • 1d Zajc B. Kumar R. Synthesis  2010,  1822 
  • 2a Gauthier JY. Chauret N. Cromlish W. Desmarais S. Duong LT. Falgueyret J.-P. Kimmel DB. Lamontagne S. Léger S. LeRiche T. Li CS. Massé F. McKay DJ. Nicoll-Griffith DA. Oballa RM. Palmer JT. Percival MD. Riendeau D. Robichaud J. Rodan GA. Rodan SB. Seto C. Thérien M. Truong V.-L. Venuti MC. Wesolowski G. Young RN. Zamboni R. Black WC. Bioorg. Med. Chem. Lett.  2008,  18:  923 
  • 2b Black WC. Bayly CI. Davis DE. Desmarais S. Falgueyret J.-P. Léger S. Li CS. Massé F. McKay DJ. Palmer JT. Percival MD. Robichaud J. Tsou N. Zamboni R. Bioorg. Med. Chem. Lett.  2005,  15:  4741 
  • For reviews on applications of the trifluoroethyl group in biochemistry, see:
  • 3a Bravo P. Bruche L. Pesenti C. Viani F. Volonterio A. Zanda M. J. Fluorine Chem.  2001,  112:  153 
  • 3b Zanda M. New J. Chem.  2004,  28:  1401 
  • 3c Sani M. Volonterio A. Zanda M. ChemMedChem  2007,  2:  1693 
  • 4a Volonterio A. Bellosta S. Bravin F. Bellucci MC. Bruche L. Colombo G. Malpezzi L. Mazzini S. Meille SV. Meli M. Arellano CR. Zanda M. Chem. Eur. J.  2003,  9:  4510 
  • 4b Molteni M. Pesenti C. Sani M. Volonterio A. Zanda M. J. Fluorine Chem.  2004,  125:  1735 
  • 4c Binkert C. Frigerio M. Jones A. Meyer S. Pesenti C. Prade L. Viani F. Zanda M. ChemBioChem  2006,  7:  181 
  • For recent reviews on the synthesis of fluorinated β-amino acids, see
  • 5a Acena JL. Simon-Fuentes A. Fustero S. Curr. Org. Chem.  2010,  14:  928 
  • 5b Mikami K. Fustero S. Sánchez-Roselló M. Acena J.-L. Soloshonok V. Sorochinsky A. Synthesis  2011,  3045 
  • 6a Bravo P. Corradi E. Pesenti C. Vergani B. Viani F. Volonterio A. Zanda M. Tetrahedron Asymmetry  1998,  9:  3731 
  • 6b Sergeeva NN. Golubev AS. Hennig L. Burger K. Synthesis  2002,  2579 
  • 6c Wan W. Hou J. Jiang H. Yuan Z. Ma G. Zhao G. Hao J. Eur. J. Org. Chem.  2010,  1778 
  • 6d Bezdudny AV. Alekseenko AN. Mykhailiuk PK. Manoilenko OV. Shishkin OV. Pustovit YM. Eur. J. Org. Chem.  2011,  1782 
  • 7a Sato K. Tarui A. Omote M. Ando A. Kumadaki I. Synthesis  2010,  1865 
  • 7b Shibata N. Matsnev A. Cahard D. Beilstein J. Org. Chem.  2010,  6:  65 
  • 7c Nie J. Guo H.-C. Cahard D. Ma J. Chem. Rev.  2011,  111:  455 
  • 8a Singh RP. Shreeve JM. Tetrahedron  2000,  56:  7631 
  • 8b Prakash GKS. Yudin AK. Chem. Rev.  1997,  97:  757 
  • Under standard conditions for the Ruppert reaction, only activated imines such as azirines, imines of perfluorinated ketones, N-sulfonylated aldimines, or nitrones react with trifluoromethyl(trimethyl)silane; see:
  • 9a Felix CP. Khatimi N. Laurent A. Tetrahedron Lett.  1994,  35:  3303 
  • 9b Banks RE. Besheesh M. Lawrence NJ. Tovell DJ. J. Fluorine Chem.  1999,  97:  79 
  • 9c Petrov VA. Tetrahedron Lett.  2000,  41:  6959 
  • 9d Kawano Y. Fujisawa H. Mukaiyama T. Chem. Lett.  2005,  34:  422 
  • 9e Nelson DW. Owens J. Hiraldo D. J. Org. Chem.  2001,  66:  2572 
  • 9f Nelson DW. Easley RA. Pintea BNV. Tetrahedron Lett.  1999,  40:  25 
  • Several uncommon examples of reactions of nonactivated imines with trifluoromethyl(trimethyl)silane have been reported; these involve the use of tetraalkylammonium fluoride or basic phosphines as initiators, the addition of(trimethylsilyl)imidazole as an activator, or the initial generation of a boron complex; see:
  • 10a Prakash GKS. Mogi R. Olah GA. Org. Lett.  2006,  8:  3589 
  • 10b Kirij NV. Babadzhanova LA. Movchun VN. Yagupolskii YL. Tyrra W. Naumann D. Fischer HTM. Scherer H. J. Fluorine Chem.  2008,  129:  14 
  • 10c Matsukawa S. Saijo M. Tetrahedron Lett.  2008,  49:  4655 
  • 10d Blazejewski J.-C. Anselmi E. Wilmshurst M. Tetrahedron Lett.  1999,  40:  5475 
  • 10e Blazejewski J.-C. Anselmi E. Wilmshurst M. Tetrahedron Lett.  1999,  40:  5475 
  • 10f Dilman AD. Arkhipov DE. Levin VV. Belyakov PA. Korlyukov AA. Struchkova MI. Tartakovsky VA. J. Org. Chem.  2007,  72:  8604 
  • 11a Levin VV. Dilman AD. Belyakov PA. Struchkova MI. Tartakovsky VA. Eur. J. Org. Chem.  2008,  5226 
  • 11b Dilman AD. Levin VV. Eur. J. Org. Chem.  2011,  831 
  • 12 The procedure reported by Dilman et al. was previously used by another research group; see: Shevchenko NE. Vlasov K. Nenajdenko VG. Röschenthaler G.-V. Tetrahedron  2011,  67:  69 
  • 13a Pigou PE. Schiesser CH. J. Org. Chem.  1988,  53:  3841 
  • 13b Radchenko DS. Mykhailiuk PK. Bezdudny AV. Komarov IV. Synlett  2009,  1827 
  • 14 Radchenko DS. Grygorenko OO. Komarov IV. Tetrahedron: Asymmetry  2008,  19:  2924 
  • For the synthesis of fluorinated GABA analogues, see:
  • 15a Silverman RB. Levy MA. J. Org. Chem.  1980,  45:  815 
  • 15b Silverman RB. Invergo BJ. Mathew J. J. Med. Chem.  1986,  29:  1840 
  • 15c Silverman RB. Nanavati SM. J. Med. Chem.  1990,  33:  931 
  • 15d Deniau G. Slawin AMZ. Lebl T. Chorki F. Issberner JP. van Mourik T. Heygate JM. Lambert JJ. Etherington L.-A. Sillar KT. O’Hagan D. ChemBioChem  2007,  8:  2265 
  • 15e Gerus II. Mironets RV. Shaitanova EN. Kukhar VP. J. Fluorine Chem.  2010,  131:  224 
  • 15f Yamazaki T. Ohnogi T. Kitazume T. Tetrahedron: Asymmetry  1990,  1:  215 
  • 15g Pan Y. Qiu J. Silverman RB. J. Med. Chem.  2003,  46:  5292 
  • 15h Zhiyong W. Silverman RB. Bioorg. Med. Chem.  2006,  14:  2242 
  • 15i Lu H. Silverman RB. J. Med. Chem.  2006,  49:  7404 
  • 16 Sheldrick GM. Acta Crystallogr., Sect. A  2008,  64:  112