PDF herunterladen
Synlett 2007(10): 1569-1572  
DOI: 10.1055/s-2007-982551
LETTER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Methanolysis of Cyclic meso-Anhydrides with Tripodal 2,6-trans-1,2,6-Trisubstituted Piperidine as Chiral Amine Catalyst

Tohru Okamatsu, Ryo Irie*, Tsutomu Katsuki
Department of Chemistry, Faculty of Science, Graduate School, Kyushu University 33, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Fax: +81(92)6422607; e-Mail: irie.scc@mbox.nc.kyushu-u.ac.jp;
Weitere Informationen

Publikationsverlauf

Received 5 March 2007
Publikationsdatum:
06. Juni 2007 (online)

   Lizenzen und Reprints Alle Artikel dieser Rubrik
Preview

Abstract

An optically active tripodal amine, (2S,6S)-2,6-bis(o-hydroxyphenyl)-1-(2-pyridylmethyl)piperidine, was proven to be a potent chiral catalyst (1-5 mol%) for methanolytic asymmetric desymmetrization of cyclic meso-anhydrides to hemiesters. A good level of enantioselectivities (up to 81% ee) was achieved for various substrates, some of which were reported to be poor substrates for methanolysis using known chiral amines as catalysts.

Key words

chiral amine catalyst - cyclic meso-anhydrides - asymmetric desymmetrization - methanolysis - organocatalysis

    References and Notes

  • 2a Dalco PI. Moisan L. Angew. Chem. Int. Ed.  2001,  40:  3726 
    Suche in Google Scholar
  • 2b Jarvo ER. Miller SJ. Tetrahedron  2002,  58:  2481 
    Suche in Google Scholar
  • 2c Dalco PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Suche in Google Scholar
  • 2d Berkessel A. Grögger H. Asymmetric Organocatalysis   Wiley-VCH; Weinheim: 2005. 
  • 2e France S. Guerin DJ. Miller SJ. Lectka T. Chem. Rev.  2003,  103:  2985 
    Suche in Google Scholar
  • 3 Chen Y. McDaid P. Deng L. Chem. Rev.  2003,  103:  2965 
    Suche in Google Scholar
  • 4a Hiratake J. Yamamoto Y. Oda J. J. Chem. Soc., Chem. Commun.  1985,  1717 
  • 4b Hiratake J. Inagaki M. Yamamoto Y. Oda J. J. Chem. Soc., Perkin Trans. 1  1987,  1053 
  • 4c Aitken RA. Gopal J. Hirst JA. J. Chem. Soc., Chem. Commun.  1988,  632 
  • 4d Bolm C. Gerlach A. Dinter CL. Synlett  1999,  195 
  • 4e Bolm C. Schiffers I. Dinter CL. Gerlach A. J. Org. Chem.  2000,  65:  6984 
    Suche in Google Scholar
  • 4f Chen Y. Tian S.-K. Deng L. J. Am. Chem. Soc.  2000,  122:  9542 
    Suche in Google Scholar
  • 4g Bolm C. Schiffers I. Atodiresei I. Hackenberger CPR. Tetrahedron: Asymmetry  2003,  14:  3455 
    Suche in Google Scholar
  • 4h Rodriguez B. Rantanen T. Bolm C. Angew. Chem. Int. Ed.  2006,  45:  6924 
    Suche in Google Scholar
  • 6 Uozumi Y. Yasoshima K. Miyachi T. Nagai S.-I. Tetrahedron Lett.  2001,  42:  411 
    Suche in Google Scholar
  • 7 Honjo T. Sano S. Shiro M. Nagao Y. Angew. Chem. Int. Ed.  2005,  44:  5838 
    Suche in Google Scholar
  • Various transition-metal-catalyzed asymmetric ring-opening reactions of cyclic meso-anhydrides were also reported:
  • 8a Seebach D. Jaeschke G. Wang YM. Angew. Chem., Int. Ed. Engl.  1995,  34:  2395 
    Suche in Google Scholar
  • 8b Shintani R. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  1057 
    Suche in Google Scholar
  • 8c Bercot EA. Rovis T. J. Am. Chem. Soc.  2002,  124:  174 
    Suche in Google Scholar
  • 8d Bercot EA. Rovis T. J. Am. Chem. Soc.  2004,  126:  10248 
    Suche in Google Scholar
  • For the related asymmetric desymmetrization of cyclic meso-anhydrides with stoichiometric chiral alcohols and amines, see:
  • 8e Ohshima M. Mukaiyama T. Chem. Lett.  1987,  377 
  • 8f Ohtani M. Matsuura T. Watanabe F. Narisada M. J. Org. Chem.  1991,  56:  4120 
    Suche in Google Scholar
  • 8g Theisen PD. Heathcock CH. J. Org. Chem.  1993,  58:  142 
    Suche in Google Scholar
  • 8h Hashimoto N. Kawamura S. Ishizuka T. Kunieda T. Tetrahedron Lett.  1996,  37:  9237 
    Suche in Google Scholar
  • 8i Jones IG. Jones W. North M. Teijeira M. Uriarte E. Tetrahedron Lett.  1997,  38:  889 
    Suche in Google Scholar
  • 8j Hibbs DE. Hursthouse MB. Jones IG. Jones W. Malic KMA. North M. J. Org. Chem.  1999,  64:  5413 
    Suche in Google Scholar
  • 8k Evans AC. Longbottom DA. Matsuoka M. Ley SV. Synlett  2005,  646 
  • 9 Okamatsu T. Irie R. Katsuki T. J. Organomet. Chem.  2007,  692:  645 
    Suche in Google Scholar
  • For the representative related studies on the helical chirality induced by tripodal tertiary amine ligands, see:
  • 10a Canary JW. Allen CS. Castagnetto JM. Wang Y. J. Am. Chem. Soc.  1995,  117:  8484 
    Suche in Google Scholar
  • 10b Dai Z. Xu X. Canary JW. Chirality  2005,  17:  S227 
    Suche in Google Scholar
  • 11 The identical architecture was also reported for achiral N,N-bis(2-hydroxybenzyl)-2-picolylamine: Vencato I. Neves A. Ceccato AS. Horn A. Acta Crystallogr., Sect. C  1996,  52:  949 
    Suche in Google Scholar
  • 12a Marcelli T. van Maarseveen JH. Hiemstra H. Angew. Chem. Int. Ed.  2006,  45:  7496 
    Suche in Google Scholar
  • 12b Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
    Suche in Google Scholar
  • 16 Mori K. Tomioka H. Fukuyo E. Yanagi K. Liebigs Ann. Chem.  1993,  671 
  • 17 Bigi F. Carloni S. Maggi R. Mazzacani A. Sartori G. Tanzi G. J. Mol. Catal. A: Chem.  2002,  182-183:  533 
    Suche in Google Scholar
1

Current address: Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan. E-mail: irie@sci.kumamoto-u.ac.jp

5

Bolm et al. also devised a catalytic system with a stoichiometric amount of sacrificial achiral amine.4e

13

Although we used the (R,R)-isomer of 1 in our previous report (ref. 8), this work was performed with (S,S)-1.

14

Typical Procedure for Catalytic Asymmetric Methanolysis of Cyclic meso-Anhydrides: To a solution or suspension of cyclic meso-anhydride (0.1 mmol) and 1 (1.8 mg, 5 µmol) in dist. toluene (1-2.5 mL) was added MeOH (20-81 µL, 0.5-2.0 mmol) at the temperature specified in Table 1 and Table 2. After being stirred at the temperature for 24 h, an aliquot of the reaction mixture was concentrated and subjected to 1H NMR analysis. The chemical yield was estimated from the ratio of the unreacted anhydride and the hemiester produced, which were the only two components in the crude reaction mixture. Then, whole the mixture was acidified with aq HCl (1 M, 1.0 mL) to extract 1 into the aqueous phase. The phases were separated and the product in the organic layer was extracted with sat. NaHCO3 (2 × 1.0 mL), leaving the starting material in the organic layer. After the organic layer was discarded, the aqueous layer was acidified with aq HCl (1 M, 2.0 mL) and extracted with EtOAc (3 × 2.0 mL). The combined organic layer was dried over Na2SO4 and concentrated in vacuo to give the desired hemiester in almost pure form judged by the 1H NMR analysis.

15

The conditions for the HPLC analysis of each compound are as follows: 3a: DAICEL CHIRALCELL AS-H, hexane-2-propanol-CF3COOH = 95:5:0.1, 0.3 mL/min. Carboxanilide of 3b: DAICEL CHIRALCELL AD-H, hexane-2-pro-
panol = 90:10, 0.5 mL/min. Carboxanilide of 3c: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 90:10, 0.5 mL/min. p-Bromophenyl ester of 3d: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 98:2, 0.5 mL/min. p-Bromo-phenyl ester of 3e: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 98:2, 0.5 mL/min. Carboxanilide of 3f: DAICEL CHIRALCELL OD-H, hexane-2-propanol = 92:8, 0.5 mL/min. 3g: DAICEL CHIRALCELL AD-H, hexane-2-propanol-CF3COOH = 90:10:0.1, 0.5 mL/min. Carboxanilide of 3h: DAICEL CHIRALCELL AS-H, hexane-2-propanol = 70:30, 0.5 mL/min. Carboxanilide of 3i: DAICEL CHIRALCELL OJ-H, hexane-2-propanol = 90:10, 0.5 mL/min.

18

The authors are grateful to a reviewer for useful suggestions about the mechanism of this reaction that is now under investigation in our laboratory.