Ferrier Glycosylation Reaction Catalyzed by Bi(OTf)3-Montmorillonite K-10: Efficient Synthesis of 3,4-Unsaturated Sialic Acid Derivatives

Kiyoshi Ikeda; Yayoi Ueno; Satoru Kitani; Reiko Nishino; Masayuki Sato

doi:10.1055/s-2008-1072649

LETTER

Ferrier Glycosylation Reaction Catalyzed by Bi(OTf)₃-Montmorillonite K-10: Efficient Synthesis of 3,4-Unsaturated Sialic Acid Derivatives

Kiyoshi Ikeda*, Yayoi Ueno, Satoru Kitani, Reiko Nishino, Masayuki Sato
School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka, 422-8526, Japan
Fax: +81(54)2645108; e-Mail: ikeda@ys2.u-shizuoka-ken.ac.jp;

Abstract

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Abstract

The reaction of the 4,5-oxazoline derivative of sialic acid with various alcohols was effectively promoted by a catalytic amount of montmorillonite K-10 clay supported Bi(OTf)₃ to produce a variety of 3,4-unsaturated sialic acids via the Ferrier glycosylation reaction in moderate yields.

Key words

Ferrier glycosylation reaction - 3,4-unsaturated sialic acid - Bi(OTf)₃-montmorillonite K-10 - 4,5-oxazoline derivative of sialic acid - sialidase inhibitor

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References

References and Notes

1 Schauer R. Kelm S. Reuter G. Roggentin P. Shaw L. Biochemistry and Role of Sialic Acids, In Biology of the Sialic Acids Rosenberg A. Plenum; New York: 1995. p.7

2 Ikeda K. Sato M. Torisawa Y. Curr. Med. Chem. 2004, 3: 339

3 von Itzstein M. Wu W.-Y. Kok GB. Pegg MS. Dyason JC. Jin B. Phan TV. Smythe ML. White HF. Oliver SW. Colman PM. Varghese JN. Ryan DM. Woods JM. Bethell RC. Hotham VJ. Cameron JM. Penn CR. Nature (London) 1993, 363: 418

4 Murphy BR. Parainfluenza viruses, In Infectious Diseases Gorbach SL. Bartlett JG. Blacklow NR. W. B. Saunders Company; Philadelphia: 1998. p.2125

5 Ferrier RJ. Prasad NJ. J. Chem. Soc. C 1969, 570

6a Fraser-Reid B. Acc. Chem. Res. 1985, 18: 347

6b Ferrier RJ. Adv. Carbohydr. Chem. Biochem. 1969, 24: 199

7a Descotes G. Martin J.-C. Carbohydr. Res. 1977, 56: 168

7b Klaffke W. Pudlo P. Springer D. Thiem J. Liebigs Ann. Chem. 1991, 509

8a Grynkiewicz G. Priebe W. Zamojski A. Carbohydr. Res. 1979, 68: 33

8b Bhate P. Horton D. Priebe W. Carbohydr. Res. 1985, 144: 331

9 Toshima K. Ishizuka T. Matsuo G. Nakata M. Synlett 1995, 306

10 Babu JL. Khare A. Vankar YD. Molecules 2005, 10: 884

11 Toshima K. Ishizuka T. Matsuo G. Nakata M. Chem. Lett. ,

12 Lopez JC. Gomez AM. Valverdi S. Fraser-Reid B.
J. Org. Chem. 1995, 60: 3851

13 Takhi M. Abdel-Rahman AA.-H. Schmidt RR. Synlett 2001, 427

14 Yadav JS. Reddy BVS. Murthy CVSR. Mahesh Kumar G. Synlett 2000, 1450

15a Ikeda K. Torisawa Y. Nishi T. Minamikawa J.-I. Tanaka K. Sato M. Bioorg. Med. Chem. 2003, 11: 3073

15b Yamanoi T. Inoue R. Matsuda S. Katsuraya K. Hamasaki K. Tetrahedron: Asymmetry 2006, 17: 2914

16 Schuff BP. Mercer GJ. Nguyen HM. Org. Lett. 2007, 9: 3173

17 Miler CA. Wang P. Flashner M. Biochem. Biophys. Res. Commun. 1978, 83: 1479

18 Jeanne M. Beatrice B. Bernard C. Christian D. Gerard Q. Alain D. Bull. Soc. Chim. Fr. 1994, 131: 400

19a Ikeda K. Sano K. Ito M. Saito M. Hidari K. Suzuki T. Suzuki Y. Tanaka K. Carbohydr. Res. 2001, 330: 31

19b Suzuki T. Ikeda K. Koyama N. Hosokawa C. Kogure T. Takahashi T. Hidari K. Miyamoto D. Tanaka K. Suzuki Y. Glycoconjugate J. 2001, 18: 331

19c Ikeda K. Kitani S. Sato K. Suzuki T. Hosokawa C. Suzuki Y. Tanaka K. Sato M. Carbohydr. Res. 2004, 339: 1367

19d Ikeda K. Sato K. Kitani S. Suzuki T. Maki N. Suzuki Y. Sato M. Bioorg. Med. Chem. 2006, 14: 7893

19e Sato K. Ikeda K. Suzuki T. Aoyama S. Maki N. Suzuki Y. Sato M. Tetrahedron 2007, 63: 7571

20 Torisawa Y. Nishi T. Minamikawa J.-I. Bioorg. Med. Chem. Lett. 2002, 12: 387

21 Zbiral E. Brandstetter HH. Christian R. Schauer R. Liebigs Ann. Chem. 1987, 781

22

The α-methyl ketoside of 5-acetamido-3,4,5-trideoxy-d-manno-non-3-en-2-ulosonic acid (4a), and its β-epimer were synthesized from 3-acetamido-4,5,6,7-tetra-O-acetyl-2,3-dideoxy-d-manno-heptose, and methyl 2-methoxy-2-dimethylphosphono acetate in 29% yield over five steps. [18]

23 Tokimoto H. Fujimoto Y. Fukase K. Kusumoto S. Tetrahedron: Asymmetry 2005, 16: 441

24

Typical Procedure
To a stirred mixture of 5 (50 mg, 0.12 mmol) and MeOH (0.1 mL) in MeCN (1.0 mL) was added 40% w/w Bi(OTf)₃-montmorillonite K-10 loading of 20% w/w of Bi(OTf)₃ (15 mg) at ambient temperature. The mixture was stirred for
20 h at r.t. The reaction suspension was filtered and the filtrate was evaporated under vacuum. The residue was purified by column chromatography on silica gel with CH₂Cl₂-MeOH (10:1) to give 4a (51 mg, 95%).
Compound 4a-α: ¹H NMR (500 MHz, CDCl₃): δ = 1.99 (s, 3 H, CH₃CONH), 2.05, 2.12, 2.14 (s, each 3 H, CH₃CO), 3.34 (s, 3 H, CH₃O), 3.78 (s, 3 H, CH₃COO), 4.24 (dd, 1 H, J _9a,9b = 12.4 Hz, J _8,9a = 5.9 Hz, H-9a), 4.26 (dd, 1 H, J _5,6 = 9.8 Hz, J _6,7 = 2.1 Hz, H-6), 4.48 (dd, 1 H, J _8,9b = 2.4 Hz, H-9b), 4.52 (dddd, J _5,NH = 9.2 Hz, J _4,5 = 2.6 Hz, J _3,5 = 1.9 Hz, H-5), 5.35 (dd, 1 H, J _7,8 = 6.1 Hz, H-7), 5.44 (ddd, 1 H, H-8), 5.59 (d, 1 H, CH₃CONH), 5.78 (dd, 1 H, J _3,4 = 10.1 Hz, H-4), 6.07 (dd, 1 H, H-3). MS-FAB (NBA): m/z = 446 [M + H]⁺, 468 [M + Na]⁺. HRMS-FAB: m/z calcd for C₁₉H₂₈NO₁₁: 446.1662; found: 446.1613.
Compound 4a-β: ¹H NMR (500 MHz, CDCl₃): δ = 1.99 (s, 3 H, CH₃CONH), 2.04, 2.10, 2.16 (s, each 3 H, CH₃CO), 3.29 (s, 3 H, CH₃O), 3.82 (s, 3 H, CH₃COO), 4.05 (dd, 1 H, J _5,6 = 10.2 Hz, J _6,7 = 2.3 Hz, H-6), 4.24 (dd, 1 H, J _9a,9b = 12.5 Hz, J _9a,8 = 6.3 Hz, H-9a), 4.63 (dd, 1 H, J _8,9b = 2.3 Hz, H-9b), 4.64 (m, 1 H, H-5), 5.35 (ddd, 1 H, J _7,8 = 5.6 Hz, H-8), 5.40 (dd, 1 H, H-7), 5.51 (d, 1 H, CH₃CONH), 5.91 (s, 2 H, H-3 and H-4).