Download PDF
Synlett 2010(6): 962-966  
DOI: 10.1055/s-0029-1219534
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

BINAP-AgSbF6 vs. BINAP-AgClO4 Complexes as Catalysts for the Enantioselective 1,3-Dipolar Cycloaddition of Azomethine Ylides and Alkenes

María Martín-Rodrígueza, Carmen Nájeraa, José M. Sansano*a, Paulo R. R. Costab, Evanoel Crizanto de Limab, Ayres G. Diasb
a Departamento de Química Orgánica e Instituto de Síntesis Orgánica (ISO), Facultad de Ciencias, Universidad de Alicante, 03080 Alicante, Spain
Fax: +34(96)5903549; e-Mail: jmsansano@ua.es;
b Laboratório de Química Biorgânica, Núcleo de Pesquisas de Produtos Naturais, Centro de Ciencias da Saúde, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-590 Rio de Janeiro, Brazil
Further Information

Publication History

Received 30 December 2009
Publication Date:
23 February 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

The employment of AgSbF6 and BINAP ligands has been evaluated in the catalyzed enantioselective 1,3-dipolar cycloadditions between azomethine ylides and electrophilic alkenes. The results are compared with the analogous ones obtained when using AgClO4. The cycloaddition with maleimides and trans-1,2-bis(phenylsulfonyl)ethylene are clearly improved by the AgSbF6-derived catalyst, and its efficiency is crucial for ensure good yields and excellent ee in the three-component reaction.

Key words

asymmetric catalysis - prolines - silver salts - azomethine ylides - multicomponent reaction

    References and Notes

  • For more general reviews of 1,3-dipolar cycloadditions, see:
  • 1a Padwa A. Bur SK. Tetrahedron  2007,  63:  5341 
    Google Scholar
  • 1b Pellisier H. Tetrahedron  2007,  63:  3235 
    Google Scholar
  • 1c Coldham I. Hufton R. Chem. Rev.  2005,  105:  2765 
    Google Scholar
  • 2 Longmire JM. Wang B. Zhang X. J. Am. Chem. Soc.  2002,  124:  13400 
    CrossrefGoogle Scholar
  • For the first enantioselective 1,3-DC catalyzed by stoichiometric amounts of Ag+ complexes, see:
  • 3a Allway P. Grigg R. Tetrahedron Lett.  1991,  32:  5817 
    Google Scholar
  • 3b Grigg R. Tetrahedron: Asymmetry  1995,  6:  2475 
    Google Scholar
  • For recent reviews, see:
  • 4a Nájera C. Sansano JM. Topics in Heterocyclic Chemistry   Hassner A. Springer; New York: . 
    Google Scholar
  • 4b Stanley LM. Sibi MP. Chem. Rev.  2008,  108:  2887 
    Google Scholar
  • 4c Álvarez-Corral M. Muñoz-Dorado M. Rodríguez-García I. Chem. Rev.  2008,  108:  3174 
    Google Scholar
  • 4d Naodovic M. Yamamoto H. Chem. Rev.  2008,  108:  3132 
    Google Scholar
  • 4e Nair V. Suja TD. Tetrahedron  2007,  63:  12247 
    Google Scholar
  • 4f Pandey G. Banerjee P. Gadre SR. Chem. Rev.  2006,  106:  4484 
    Google Scholar
  • 4g Pinho e Melo TMVD. Eur. J. Org. Chem.  2006,  2873 
    Google Scholar
  • 4h Bonin M. Chauveau A. Micouin L. Synlett  2006,  2349 
    Google Scholar
  • 4i Nájera C. Sansano JM. Angew. Chem.  2005,  44:  6272 
    Google Scholar
  • 4j Husinec S. Savic V. Tetrahedron: Asymmetry  2005,  16:  2047 
    Google Scholar
  • For recent reviews on asymmetric synthesis of α-amino acids, see:
  • 5a Nájera C. Sansano JM. Chem. Rev.  2007,  107:  4273 
    Google Scholar
  • 5b Calaza MI. Cativiela C. Eur. J. Org. Chem.  2008,  3427 
    Google Scholar
  • 6a Chen C. Li X. Schreiber SL. J. Am. Chem. Soc.  2003,  125:  10174 
    Google Scholar
  • 6b Knöpfel TF. Aschwanden P. Ichikawa T. Watanabe T. Carreira EM. Angew. Chem. Int. Ed.  2004,  43:  5971 
    Google Scholar
  • 6c Zheng W. Zhou Y.-G. Org. Lett.  2005,  7:  5055 
    Google Scholar
  • 6d Stohler R. Wahl F. Pfaltz A. Synthesis  2005,  1431 
    Google Scholar
  • 6e Zheng W. Zhou Y.-G. Tetrahedron Lett.  2007,  48:  4619 
    Google Scholar
  • 6f Zheng W. Chen G.-Y. Zhou YG. Li Y.-X. J. Am. Chem. Soc.  2007,  129:  750 
    Google Scholar
  • 6g Nájera C. Retamosa MG. Sansano JM. Angew. Chem. Int. Ed.  2008,  47:  6055 
    Google Scholar
  • 6h Nájera C. Retamosa MG. Martín-Rodríguez M. Sansano JM. de Cózar A. Cossío FP. Eur. J. Org. Chem.  2009,  5622 
    Google Scholar
  • 6i Yu SB. Hu X.-P. Deng J. Wang D.-Y. Duan Z.-C. Zheng Z. Tetrahedron: Asymmetry  2009,  20:  621 
    Google Scholar
  • 7a Nájera C. Retamosa MG. Sansano JM. Org. Lett.  2007,  9:  4025 
    Google Scholar
  • 7b Nájera C. Retamosa MG. Sansano JM. de Cózar A. Cossío FP. Tetrahedron: Asymmetry  2008,  19:  2913 
    Google Scholar
  • 8a Gao W. Zhang X. Raghunath M. Org. Lett.  2005,  7:  4241 
    Google Scholar
  • 8b Cabrera S. Gómez-Arrayás R. Carretero JC. J. Am. Chem. Soc.  2005,  127:  16394 
    Google Scholar
  • 8c Yan X.-X. Peng Q. Zhang Y. Zhang K. Hong W. Hou X.-L. Wu Y.-D. Angew Chem. Int. Ed.  2006,  45:  1979 
    Google Scholar
  • 8d Llamas T. Gómez-Arrayás R. Carretero JC. Org. Lett.  2006,  8:  1795 
    Google Scholar
  • 8e Llamas T. Gómez-Arrayás R. Carretero JC. Synthesis  2007,  950 
    Google Scholar
  • 8f Shi J.-W. Shi JW. Tetrahedron: Asymmetry  2007,  18:  645 
    Google Scholar
  • 8g Martín-Matute B. Pereira SI. Peña-Cabrera E. Adrio JA. Silva MS. Carretero JC. Adv. Synth. Catal.  2007,  349:  1714 
    Google Scholar
  • 8h Cabrera S. Gómez-Arrayás R. Martín-Matute B. Cossío FP. Carretero JC. Tetrahedron  2007,  63:  6587 
    Google Scholar
  • 8i López-Pérez A. Adrio J. Carretero JC. J. Am. Chem. Soc.  2008,  130:  10084 
    Google Scholar
  • 8j Fukuzawa S. Oki HZY. Org. Lett.  2008,  10:  1747 
    Google Scholar
  • 8k Wang C.-J. Liang G. Xue ZY. Gao F.
    J. Am. Chem. Soc.  2008,  130:  17250 
    Google Scholar
  • 8l Kim HY. Shih H.-J. Knabe WE. Oh K. Angew. Chem. Int. Ed.  2009,  48:  7420 
    Google Scholar
  • 8m López-Pérez A. Adrio J. Carretero JC. Angew. Chem. Int. Ed.  2009,  48:  340 
    Google Scholar
  • 8n Hernández-Toribio J. Gómez-Arrayás R. Martín-Matute B. Carretero JC. Org. Lett.  2009,  11:  393 
    Google Scholar
  • 8o Wang C.-J. Xue ZY. Liang G. Lu Z. Chem. Commun.  2009,  2905 
    Google Scholar
  • 8p For copper(II)-catalyzed 1,3-dipolar cycloadditions, see: Oderaotoshi Y. Cheng W. Fujitomi S. Kasano Y. Minakata S. Komatsu M. Org. Lett.  2003,  5:  5043 
    Google Scholar
  • 9a Gothelf AS. Gothelf KV. Hazell RG. Jørgensen KA. Angew. Chem. Int. Ed.  2002,  41:  4236 
    Google Scholar
  • 9b Dogan O. Koyuncu H. G arner P. Bulut A. Youngs WJ. Panzner M. Org. Lett.  2006,  8:  4687 
    Google Scholar
  • 10 Shi J.-W. Zhao M.-X. Lei Z.-Y. Shi M. J. Org. Chem.  2008,  73:  305 
    CrossrefPubMedGoogle Scholar
  • 11a Saito S. Tsubogo T. Kobayashi S. J. Am. Chem. Soc.  2007,  129:  5364 
    Google Scholar
  • 11b Tsubogo T. Saito S. Seki K. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2008,  130:  13321 
    Google Scholar
  • The employment of organocatalysts has been reported:
  • 12a Alemparte C. Blay G. Jørgensen KA. Org. Lett.  2005,  7:  4569 
    Google Scholar
  • 12b Arai S. Takahashi F. Tsuji R. Nishida A. Heterocycles  2006,  67:  495 
    Google Scholar
  • 12c Ibrahem I. Ríos R. Vesely J. Córdova A. Tetrahedron Lett.  2007,  48:  6252 
    Google Scholar
  • 12d Xue M.-X. Zhang X.-M. Gong L.-Z. Synlett  2008,  691 
    Google Scholar
  • 12e Vicario JL. Reboredo S. Badía D. Carrillo L. Angew. Chem. Int. Ed.  2007,  46:  5168 
    Google Scholar
  • 12f Agbodjan AA. Cooley BE. Copley RCB. Corfield JA. Flanagan RC. Glover BN. Guidetti R. Haigh D. Howes PD. Jackson MM. Matsuoka RT. Medhurst KJ. Millar A. Sharp MJ. Slater MJ. Toczko JF. Xie S. J. Org. Chem.  2008,  73:  3094 
    Google Scholar
  • 12g Flanagan RC. Xie S. Millar A. Org. Process Res. Dev.  2008,  12:  1307 
    Google Scholar
  • 12h Nakano M. Terada M. Synlett  2009,  1670 
    Google Scholar
  • 12i Yu LHeL. Chen X.-H. Song J. Chen W.-J. Gong L.-Z. Org. Lett.  2009,  11:  4946 
    Google Scholar
  • 12j Chen X.-H. Zhang W.-Q. Gong L.-Z. J. Am. Chem. Soc.  2009,  130:  5652 
    Google Scholar
  • 12k Chen X.-H. Wei Q. Luo S.-W. Xiao H. Gong L.-Z. J. Am. Chem. Soc.  2009,  130:  13819 
    Google Scholar
  • 13 For a recent review about Lewis acid vs. organocatalytic asymmetric 1,3-DC, see: Nájera C. Sansano JM. Yus M. J. Braz. Chem. Soc.  2009,  in press
    Google Scholar
  • 14 Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  5360 
    CrossrefGoogle Scholar
15

The BINAP-AgSbF6 (2:1) chiral cluster was not characterized because it afforded lower endo/exo diastereoselectivity, such as occurred in the previously reported chiral BINAP-AgClO4-catalyzed 1,3-DC (ref. 7).

16

General Procedure for the Catalytic Enantioselective 1,3-DC Using Silver Salts
A solution of the imino ester (1 mmol) and dipolarophile
(1 mmol) in toluene (5 mL) was added to a suspension containing (R)- or (S)-BINAP (0.05 mmol, 31 mg) and silver(I) salt (0.05 mmol) in toluene (5 mL). To the resulting suspension Et3N (0.05 mmol, 7 µL) was added and the mixture stirred at r.t. and in the absence of the light for 16-48 h (see main text). The reaction was filtered, the organic filtrate was directly evaporated, and the residue was purified by recrystallization or by flash chromatography yielding pure endo cycloadducts.
General Procedure for the Three-Component Catalytic Enantioselective 1,3-DC Using Silver Salts
To a suspension containing (R)- or (S)-BINAP (0.05 mmol, 31 mg) and AgSbF6 (0.05 mmol, 17 mg) in toluene (10 mL) was added the freshly distilled aldehyde (1 mmol), glycine methyl ester hydrochloride (1 mmol), the dipolarophile (1 mmol), and Et3N (140 µL, 1.05 mmol). The mixture was stirred at r.t. and in the absence of the light for 16-48 h (see main text). Following the same workup as that described above, final cycloadducts 3aa and 8c were obtained.