Download PDF
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
Further Information

Publication History

Received 15 October 2010
Publication Date:
13 January 2011 (online)

   Permissions and Reprints All articles of this category
Preview

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