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Synlett 2009(20): 3279-3282  
DOI: 10.1055/s-0029-1218374
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Chiral Bifunctional Sulfonamide as an Organocatalyst: Alcoholysis of σ-Symmetric Cyclic Dicarboxylic Anhydrides

Takashi Honjoa, Takeshi Tsumuraa, Shigeki Sano*a, Yoshimitsu Nagaoa, Kentaro Yamaguchib, Yoshihisa Seib
a Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Fax: +81(88)6339503; e-Mail: ssano@ph.tokushima-u.ac.jp;
b Faculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan
Further Information

Publication History

Received 8 September 2009
Publication Date:
18 November 2009 (online)

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Abstract

Enantioselective alcoholysis of σ-symmetric cyclic dicarboxylic anhydrides with benzyl alcohol catalyzed by a chiral bifunctional sulfonamide was achieved in up to 98% ee at 5 mol% loading.

Key words

anhydrides - asymmetric synthesis - homogeneous catalysis - sulfonamides - alcoholysis

    References and Notes

  • For recent reviews on enzymes in organic chemistry, see:
  • 1a Suga T. Curr. Org. Chem.  1999,  3:  377 
    Google Scholar
  • 1b Koeller KM. Wong C.-H. Nature (London)  2001,  409:  232 
    Google Scholar
  • 1c Sheldon RA. van Rantwijk F. Aust. J. Chem.  2004,  57:  281 
    Google Scholar
  • 1d Sureshkumar M. Lee C.-K. J. Mol. Catal. B: Enzym.  2009,  60:  1 
    Google Scholar
  • For recent reviews on organocatalysts, see:
  • 2a Ooi T. Maruoka K. Acc. Chem. Res.  2004,  37:  526 
    Google Scholar
  • 2b Tian S.-K. Chen Y. Hang J. Tang L. McDaid P. Deng L. Acc. Chem. Res.  2004,  37:  621 
    Google Scholar
  • 2c Kobayashi S. Sugiura M. Ogawa C. Adv. Synth. Catal.  2004,  346:  1023 
    Google Scholar
  • 2d Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Google Scholar
  • 2e Dalaigh CO. Synlett  2005,  875 
    Google Scholar
  • 2f Gaunt MJ. Johansson CCC. McNally A. Vo NT. Drug Discovery Today  2006,  12:  8 
    Google Scholar
  • 2g Lelais G. MacMillan DWC. Aldrichimica Acta  2006,  39:  79 
    Google Scholar
  • 2h Imada Y. Naota T. Chem. Rec.  2007,  7:  354 
    Google Scholar
  • 2i Buckley BR. Annu. Rep. Prog. Chem., Sect. B: Org. Chem.  2007,  103:  90 
    Google Scholar
  • 2j McGarrigle EM. Myers EL. Illa O. Shaw MA. Riches SL. Aggarwal VK. Chem. Rev.  2007,  107:  5841 
    Google Scholar
  • 2k Guillena G. Najera C. Ramon DJ. Tetrahedron: Asymmetry  2007,  18:  2249 
    Google Scholar
  • 2l Marion N. Díez-González S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 
    Google Scholar
  • 2m You S.-L. Chem. Asian J.  2007,  2:  820 
    Google Scholar
  • 2n Renaud P. Leong P. Science  2008,  322:  55 
    Google Scholar
  • 2o MacMillan DWC. Nature (London)  2008,  455:  304 
    Google Scholar
  • 2p Barbas CF. Angew. Chem. Int. Ed.  2008,  47:  42 
    Google Scholar
  • 2q Chen Y.-C. Synlett  2008,  1919 
    Google Scholar
  • 2r Gruttadauria M. Giacalone F. Noto R. Chem. Soc. Rev.  2008,  37:  1666 
    Google Scholar
  • 2s Xu L.-W. Luo J. Lu Y. Chem. Commun.  2009,  1807 
    Google Scholar
  • 2t Yoshioka E. Kohtani S. Miyabe H. Heterocycles  2009,  79:  229 
    Google Scholar
  • 2u Connon SJ. Synlett  2009,  354 
    Google Scholar
  • For reviews on desymmetrization of cyclic anhydrides, see:
  • 3a Spivey AC. Andrews BI. Angew. Chem. Int. Ed.  2001,  40:  3131 
    Google Scholar
  • 3b Chen Y. McDaid P. Deng L. Chem. Rev.  2003,  103:  2965 
    Google Scholar
  • 3c Atodiresei I. Schiffers I. Bolm C. Chem. Rev.  2007,  107:  5683 
    Google Scholar
  • 4a Rho HS. Oh SH. Lee JW. Lee JY. Chin J. Song CE. Chem. Commun.  2008,  1208 
    Google Scholar
  • 4b Oh SH. Rho HS. Lee JW. Lee JE. Youk SH. Chin J. Song CE. Angew. Chem. Int. Ed.  2008,  47:  7872 
    Google Scholar
  • 5 Peschiulli A. Gun’ko Y. Connon SJ. J. Org. Chem.  2008,  73:  2454 
    CrossrefPubMedGoogle Scholar
  • 6 Wang S.-X. Chen F.-E. Adv. Synth. Catal.  2009,  351:  547 
    CrossrefGoogle Scholar
  • 7 Honjo T. Sano S. Shiro M. Nagao Y. Angew. Chem. Int. Ed.  2005,  44:  5838 
    CrossrefGoogle Scholar
  • 8a Henderson R. J. Mol. Biol.  1970,  54:  341 
    Google Scholar
  • 8b Perona JJ. Craik CS. Protein Sci.  1995,  4:  337 
    Google Scholar
  • 8c Perona JJ. Craik CS. J. Biol. Chem.  1997,  272:  29987 
    Google Scholar
  • 8d Silverman RB. In The Organic Chemistry of Enzyme-Catalyzed Reactions   Academic Press; San Diego: 2000.  p.39 
    Google Scholar
  • 8e Malthouse JPG. Biochem. Soc. Trans.  2007,  35:  566 
    Google Scholar
  • 10 Zhu L.-M. Tedford MC. Tetrahedron  1990,  46:  6587 
    CrossrefGoogle Scholar
  • 12 Yamaguchi K. J. Mass Spectrom.  2003,  38:  473 
    CrossrefGoogle Scholar
  • 13 Yu X. Wang W. Chem. Asian J.  2008,  3:  516 
    CrossrefPubMedGoogle Scholar
9

General Experimental Procedure for Chiral Sulfonamide 1 Catalyzed Alcoholysis of Cyclic Dicarboxylic Anhydrides
To a solution of 3-phenylglutaric anhydride (2a, 190 mg, 1.0 mmol) and chiral sulfonamide 1 (25.8 mg, 0.05 mmol) in Et2O (10 mL) was added BnOH (125 µL, 1.2 mmol) at r.t. After stirring at r.t. for 20 h, the reaction mixture was treated with 10% HCl followed by extraction with CHCl3. The extract was dried over anhyd MgSO4, filtered, and concentrated in vacuo. To a solution of the residue in benzene-MeOH (7:2, 9 mL) was added a solution of TMSCHN2 (2.0 M in Et2O, 1 mL, 2.0 mmol). After being stirred at r.t. for 15 min, the reaction mixture was evaporated in vacuo. The oily residue was purified by silica gel column chromatography [EtOAc-n-hexane (1:4)] to afford methyl ester (S)-4a (286 mg, 92% yield, 87% ee) as a colorless oil. The ee (%) of (S)-4a was determined on a Chiralpak AD-H column [Daicel, eluent: n-hexane-2-PrOH (15:1), flow rate: 1 mL/min, detection: 254 nm]. The retention times were 12.5 min [minor isomer, (R)-4a] and 13.8 min [major isomer, (S)-4a], respectively. The absolute configuration of (S)-4a was explicitly determined by its chemical conversion to thioester (S)-5 (Scheme  [¹] ). [7]

Scheme1

11

For details see Supporting Information.