PDF herunterladen
Synlett 2011(3): 410-414  
DOI: 10.1055/s-0030-1259317
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

β-Aminosulfonamide-Catalyzed Direct Asymmetric Aldol Reaction in Brine

Tsuyoshi Miura*a, Mariko Inaa, Kie Imaia, Kosuke Nakashimaa, Akira Masudaa, Norihiro Tadaa, Nobuyuki Imaib, Akichika Itoha
a Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan
Fax: +81(58)2308105; e-Mail: miura@gifu-pu.ac.jp;
b Faculty of Pharmacy, Chiba Institute of Science, 15-8 Shiomi-cho, Choshi, Chiba 288-0025, Japan
Weitere Informationen

Publikationsverlauf

Received 15 October 2010
Publikationsdatum:
13. Januar 2011 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Direct asymmetric aldol reactions of aldehydes with ketones in the presence of a catalytic amount of β-aminosulfonamide 2 and trifluoroacetic acid in brine results in the formation of the corresponding anti-aldol products in high yields with up to 96% enantiomeric excess. The anti-aldol products obtained by using organocatalyst 2 have the opposite absolute configuration to those obtained using the similar sulfonamide catalyst 1, which was reported previously by us.

Key words

organocatalyst - aldol reaction - sulfonamide - brine - asymmetric

    References and Notes

  • For selected reviews on organocatalysis, see:
  • 1a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Google Scholar
  • 1b Pellissier H. Tetrahedron  2007,  63:  9267 
    Google Scholar
  • 1c Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev.  2007,  107:  5471 
    Google Scholar
  • 1d Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 
    Google Scholar
  • 1e Lattanzi A. Chem. Commun.  2009,  1452 
    Google Scholar
  • 1f Liu X. Lin L. Feng X. Chem. Commun.  2009,  6145 
    Google Scholar
  • 2 Modern Aldol Reactions   Vol. 1 and 2:  Mahrwald R. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • For selected reviews on organocatalysis in water, see:
  • 3a Gruttadauria M. Giacalone F. Noto R. Adv. Synth. Catal.  2009,  351:  33 
    Google Scholar
  • 3b Paradowska J. Stodulski M. Mlynarski J. Angew. Chem. Int. Ed.  2009,  48:  4288 
    Google Scholar
  • 3c Raj M. Singh K. Chem. Commun.  2009,  6687 
    Google Scholar
  • For selected recent examples of organocatalyzed aldol reactions in water, see:
  • 3d An Y.-J. Zhang Y.-X. Wu Y. Liu Z.-M. Pi C. Tao J.-C. Tetrahedron: Asymmetry  2010,  21:  688 
    Google Scholar
  • 3e Zhang S.-P. Fu X.-K. Fu S.-D. Tetrahedron Lett.  2009,  50:  1173 
    Google Scholar
  • 3f Zhou H. Xie Y. Ren L. Wang K. Adv. Synth. Catal.  2009,  351:  1284 
    Google Scholar
  • 3g Ma X. Da C S. Yi L. Jia Y.-N. Guo Q.-P. Che L.-P. Wu F.-C. Wang J.-R. Li W.-P. Tetrahedron: Asymmetry  2009,  20:  1419 
    Google Scholar
  • 3h Chimni SS. Singh S. Kumar A. Tetrahedron: Asymmetry  2009,  20:  1722 
    Google Scholar
  • 3i Fu S.-D. Fu X.-K. Zhang S.-P. Zou X.-C. Wu X.-J. Tetrahedron: Asymmetry  2009,  20:  2390 
    Google Scholar
  • 3j Vishnumaya MR. Singh VK. J. Org. Chem.  2009,  74:  4289 
    Google Scholar
  • 3k Nisco MD. Pedatella S. Ullah H. Zaidi JH. Naviglio D. Ozdamar O. Caputo R. J. Org. Chem.  2009,  74:  9562 
    Google Scholar
  • 3l Vishnumaya MR. Singh VK. J. Org. Chem.  2009,  74:  4289 
    Google Scholar
  • 3m Mase N. Noshiro N. Mokuya A. Takabe K. Adv. Synth. Catal.  2009,  351:  2791 
    Google Scholar
  • 3n Tea Y.-C. Lee PP. Synth. Commun.  2009,  39:  3081 
    Google Scholar
  • 3o Jia Y.-N. Wu F.-C. Ma X. Zhu G.-J. Da C S. Tetrahedron Lett.  2009,  50:  3059 
    Google Scholar
  • 3p Ramasastry SSV. Albertshofer K. Utsumi N. Barbas CF. Org. Lett.  2008,  10:  1621 
    Google Scholar
  • 3q Zhu M.-K. Xu X.-Y. Gong L.-Z. Adv. Synth. Catal.  2008,  350:  1390 
    Google Scholar
  • 3r Zu L. Xie H. Li H. Wang J. Wang W. Org. Lett.  2008,  10:  1211 
    Google Scholar
  • 3s Gandhi S. Singh VK. J. Org. Chem.  2008,  73:  9411 
    Google Scholar
  • 3t Zhao J.-F. He L. Jiang J. Tang Z. Cun L.-F. Gong L.-Z. Tetrahedron Lett.  2008,  49:  3372 
    Google Scholar
  • 3u Huang W.-P. Chen J.-R. Li X.-Y. Cao Y.-J. Xiao W.-J. Can. J. Chem.  2007,  85:  208 
    Google Scholar
  • 3v Huang J. Zhang X. Armstrong DW. Angew. Chem. Int. Ed.  2007,  46:  9073 
    Google Scholar
  • 3w Gryko D. Saletra WJ. Org. Biomol. Chem.  2007,  5:  2148 
    Google Scholar
  • 3x Hayashi Y. Sumiya T. Takahashi J. Gotoh H. Urushima T. Shoji M. Angew. Chem. Int. Ed.  2006,  45:  958 
    Google Scholar
  • 3y Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 
    Google Scholar
  • 4 Nakayama K. Maruoka K. J. Am. Chem. Soc.  2008,  130:  17666 
    CrossrefGoogle Scholar
  • 5 Miura T. Yasaku Y. Koyata N. Murakami Y. Imai N. Tetrahedron Lett.  2009,  50:  2632 
    CrossrefGoogle Scholar
  • 6 Miura T. Imai K. Ina M. Tada N. Imai N. Itoh A. Org. Lett.  2010,  12:  1620 
    CrossrefGoogle Scholar
  • 7 Imai N. Nokami J. Nomura T. Ninomiya Y. Shinobe A. Matsushiro S. Bull. Okayama Univ. Sci.  2002,  47 
    Google Scholar
  • 9a Bassan A. Zou W. Reues E. Himo F. Córdova A. Angew. Chem. Int. Ed.  2005,  44:  7028 
    Google Scholar
  • 9b Dziedzic P. Zou W. Háfren J. Córdova A. Org. Biomol. Chem.  2006,  4:  38 
    Google Scholar
  • 10 Mase N. Watanabe K. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  4966 
    CrossrefPubMedGoogle Scholar
  • 11 We assume that the aldol reactions are accelerated by the use of brine (salting-out effect),¹0 see: Maya V. Singh VK. Org. Lett.  2007,  9:  1117 
    CrossrefGoogle Scholar
8

A typical procedure for the aldol condensation using 2 and 6a is as follows: To a colorless suspension of p-nitro-benzaldehyde (6a; 90.7 mg, 0.600 mmol) and the organo-catalyst 2 (33.9 mg, 0.120 mmol) in brine (1.2 mL), were added cyclohexanone (0.62 mL, 6.00 mmol) and TFA (2.2 µL, 0.030 mmol) at r.t. The reaction mixture was stirred at r.t. for 36 h, and extracted three times with EtOAc. The organic layers were combined, washed with brine, dried over anhydrous MgSO4, and evaporated. The residue was purified by flash column chromatography on silica gel (toluene-EtOAc, 4:1) to afford pure 8a (121.3 mg, 81%) as a colorless solid.