1030
K. Ikeda et al.
LETTER
(12) Lopez, J. C.; Gomez, A. M.; Valverdi, S.; Fraser-Reid, B.
J. Org. Chem. 1995, 60, 3851.
(13) Takhi, M.; Abdel-Rahman, A. A.-H.; Schmidt, R. R. Synlett
2001, 427.
(14) Yadav, J. S.; Reddy, B. V. S.; Murthy, C. V. S. R.; Mahesh
Kumar, G. Synlett 2000, 1450.
OH
HO
OMe
H
a
O
CO2H
4a
HO
AcHN
7
(15) (a) Ikeda, K.; Torisawa, Y.; Nishi, T.; Minamikawa, J.-I.;
Tanaka, K.; Sato, M. Bioorg. Med. Chem. 2003, 11, 3073.
(b) Yamanoi, T.; Inoue, R.; Matsuda, S.; Katsuraya, K.;
Hamasaki, K. Tetrahedron: Asymmetry 2006, 17, 2914.
(16) Schuff, B. P.; Mercer, G. J.; Nguyen, H. M. Org. Lett. 2007,
9, 3173.
Scheme 4 Reagents and conditions: (a) (i) NaOMe, MeOH, r.t.,
15 h, 92%; (ii) 0.1 M KOH, MeOH, r.t., 15 h, quant.
higher yields in the Ferrier glycosylation reaction. We be-
lieve that this synthesis method provides a practical route
to establish novel 3,4-unsaturated sialic acid analogues.
The use of inexpensive and readily accessible Bi(OTf)3
with high yields makes it a useful and attractive alterna-
tive to the more expensive lanthanide triflate or stoichio-
metric conventional Lewis acid promoted O-
glycosidation procedures.
(17) Miler, C. A.; 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.
(19) (a) Ikeda, K.; Sano, K.; Ito, M.; Saito, M.; Hidari, K.;
Suzuki, T.; Suzuki, Y.; Tanaka, K. Carbohydr. Res. 2001,
330, 31. (b) 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.
(c) Ikeda, K.; Kitani, S.; Sato, K.; Suzuki, T.; Hosokawa, C.;
Suzuki, Y.; Tanaka, K.; Sato, M. Carbohydr. Res. 2004, 339,
1367. (d) Ikeda, K.; Sato, K.; Kitani, S.; Suzuki, T.; Maki,
N.; Suzuki, Y.; Sato, M. Bioorg. Med. Chem. 2006, 14,
7893. (e) 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.
We are currently applying this methodology to the devel-
opment of new hPIV-1 inhibitors.
Acknowledgment
We thank Dr. Kimio Furuhata (Kitazato University) for helpful dis-
cussion and encouragement. This work was financially supported in
part by a Grant-in-Aid for Scientific Research No. 19590103 from
the Ministry of Education, Science, Sports, and Culture of Japan.
The authors thank Dr. Yasuhiro Torisawa (Takasaki University of
Health and Welfare) for the generous gift of Bi(OTf)3. The authors
thank JAPAN FOOD & LIQUOR ALLIANCE INC. (Kyoto, Japan)
for the generous gift of Neu5Ac.
(21) Zbiral, E.; Brandstetter, H. H.; Christian, R.; Schauer, R.
Liebigs Ann. Chem. 1987, 781.
(22) The a-methyl ketoside of 5-acetamido-3,4,5-trideoxy-D-
manno-non-3-en-2-ulosonic acid (4a), and its b-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.
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., Ed.; Plenum: New York, 1995,
7.
(2) Ikeda, K.; Sato, M.; Torisawa, Y. Curr. Med. Chem. 2004, 3,
339.
(3) von Itzstein, M.; Wu, W.-Y.; Kok, G. B.; Pegg, M. S.;
Dyason, J. C.; Jin, B.; Phan, T. V.; Smythe, M. L.; White, H.
F.; Oliver, S. W.; Colman, P. M.; Varghese, J. N.; Ryan, D.
M.; Woods, J. M.; Bethell, R. C.; Hotham, V. J.; Cameron,
J. M.; Penn, C. R. Nature (London) 1993, 363, 418.
(4) Murphy, B. R. Parainfluenza viruses, In Infectious
Diseases; Gorbach, S. L.; Bartlett, J. G.; Blacklow, N. R.,
Eds.; W. B. Saunders Company: Philadelphia, 1998, 2125.
(5) Ferrier, R. J.; Prasad, N. J. J. Chem. Soc. C 1969, 570.
(6) (a) Fraser-Reid, B. Acc. Chem. Res. 1985, 18, 347.
(b) Ferrier, R. J. Adv. Carbohydr. Chem. Biochem. 1969, 24,
199.
(7) (a) Descotes, G.; Martin, J.-C. Carbohydr. Res. 1977, 56,
168. (b) Klaffke, W.; Pudlo, P.; Springer, D.; Thiem, J.
Liebigs Ann. Chem. 1991, 509.
(8) (a) Grynkiewicz, G.; Priebe, W.; Zamojski, A. Carbohydr.
Res. 1979, 68, 33. (b) 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, J. L.; Khare, A.; Vankar, Y. D. Molecules 2005, 10,
884.
(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-a: 1H NMR (500 MHz, CDCl3): d = 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,
J9a,9b = 12.4 Hz, J8,9a = 5.9 Hz, H-9a), 4.26 (dd, 1 H,
J5,6 = 9.8 Hz, J6,7 = 2.1 Hz, H-6), 4.48 (dd, 1 H, J8,9b = 2.4
Hz, H-9b), 4.52 (dddd, J5,NH = 9.2 Hz, J4,5 = 2.6 Hz,
J3,5 = 1.9 Hz, H-5), 5.35 (dd, 1 H, J7,8 = 6.1 Hz, H-7), 5.44
(ddd, 1 H, H-8), 5.59 (d, 1 H, CH3CONH), 5.78 (dd, 1 H,
J3,4 = 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-b: 1H NMR (500 MHz, CDCl3): d = 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,
J5,6 = 10.2 Hz, J6,7 = 2.3 Hz, H-6), 4.24 (dd, 1 H, J9a,9b = 12.5
Hz, J9a,8 = 6.3 Hz, H-9a), 4.63 (dd, 1 H, J8,9b = 2.3 Hz, H-9b),
4.64 (m, 1 H, H-5), 5.35 (ddd, 1 H, J7,8 = 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).
(11) Toshima, K.; Ishizuka, T.; Matsuo, G.; Nakata, M. Chem.
Lett. .
Synlett 2008, No. 7, 1027–1030 © Thieme Stuttgart · New York