COMMUNICATIONS
Scheme 7. Formation of 19, a mimetic of methyl a-l-idopyranoside 20, by
deprotection of compound 18: a) H2 (170 kPa), Pd/C, ethyl acetate/
methanol 1/1, RT, 2 h.
represent the first two members of a new class of synthetic
carbasugars, which are now available for various biological
studies.
Received: February 11, 2000 [Z14684]
Scheme 3. a) BnBr (6 equiv), NaH (8 equiv), DMF, RT, 2.5 h, quant;
b) TMSOTf (cat.), Ac2O, CH2Cl2 (dry), À55 to À508C, 1.5 h; c) NaOMe/
MeOH, 2 h, quant; d) PCC (1.1 equiv), 4 molecular sieves, CH2Cl2 (dry),
08C, 2 h; e) BuLi (3 equiv), Ph3PCH3Br (3 equiv), THF (dry), À788C to
RT, 1.5 h; f) TfOH/AcOH/H2O (1/28/5), 808C, 2.5 h; g) PCC (3 equiv), 4
MS, CH2Cl2 (dry), 08C to RT, 3 h; h) Tebbe reagent (3 equiv), Py/THF (1/
1), À788C to RT, 30 min; i) iBu3Al, toluene, 508C, 30 min. Abbreviations:
RT room temperature; TMS trimethylsilyl; Tf trifluoromethanesul-
fonyl; PCC pyridinium chlorochromate; Py pyridine.
[1] a) C. A. A. von Boeckel, M. Petitou, Angew. Chem. 1993, 105, 1741 ±
1750; Angew. Chem. Int. Ed. Engl. 1993, 32, 1671 ± 1690; b) Complex
Carbohydrates in Drug Research (Eds.: K. Bock, H. Clausen),
Munksgaard, 1994 (Alfred Benzon symposium 36); c) D. Zopf, S.
Roth, The Lancet 1996, 347, 1017± 1021; d) Glycoscience (Eds.: H.
Â
Driguez, J. Thiem), Springer, Berlin, 1997; e) M. Petitou, J.-P. Herault,
A. Bernat, P.-A. Driguez, P. Duchaussoy, J.-C. Lormeau, J.-M.
Herbert, Nature 1999, 398, 417± 422; f) P.-A. Driguez, I. Lederman,
J.-M. Strassel, J.-M. Herbert, M. Petitou, J. Org. Chem. 1999, 64,
9512 ± 9520.
Â
Â
[2] a) D. H. R. Barton, S. D. Gero, J. Cleophax, A. S. Machado, B.
Quiclet-Sire, J. Chem. Soc. Chem. Commun. 1988, 1184 ± 1186; b) T.
Suami, S. Ogawa, Adv. Carbohydr. Chem. Biochem. 1990, 48, 21 ± 90;
c) J. Marco-Contelles, C. Pozuelo, M. L. Jimeno, L. Martinez, A.
Martinez-Grau, J. Org. Chem. 1992, 57, 2625 ± 2631; d) S. Ogawa in
Carbohydrate Mimics, Concepts and Methods (Ed.: Y. Chapleur),
WILEY-VCH, Weinheim, 1998, pp. 87± 106; e) Y.-Q. Tang, C. Maul,
R. Höfs, I. Sattler, S. Grabley, X.-Z. Feng, A. Zeeck, R. Thiericke, Eur.
J. Org. Chem. 2000, 149 ± 153.
[3] a) F. A. L. Anet, M. St. Jacques, J. Am. Chem. Soc. 1966, 88, 2585 ±
2586; b) J. E. Anderson, E. S. Glazer, D. L. Griffith, R. Knorr, J. D.
Roberts, J. Am. Chem. Soc. 1969, 91, 1386 ± 1395; c) F. A. L. Anet, J.
Krane, Tetrahedron Lett. 1973, 5029 ± 5032; d) D. M. Pawar, E. M.
Moody, E. A. Noe, J. Org. Chem. 1999, 64, 4586 ± 4589.
[4] J. F. Stoddart, Stereochemistry of Carbohydrates, Wiley-Interscience,
New York, 1971.
Scheme 4. a) NaH, MeI (2.8 equiv), DMF, RT, 2 h; b) 1) BH3 ´ THF
(2 equiv), THF, RT, 1 h; 2) aq. NaOH (11%), aq. H2O2 (35%), 08C to
RT, 1.5 h.
[5] a) L. A. Paquette, D. Friedrich, R. D. Rogers, J. Org. Chem. 1991, 56,
3841 ± 3849; b) L. A. Paquette, C. M. G. Philippo, N. H. Vo, Can. J.
Chem. 1992, 70, 1356 ± 1365, and references therein.
[6] B. Werschkun, J. Thiem, Angew. Chem. 1997, 109, 2905 ± 2906; Angew.
Chem. Int. Ed. Engl. 1997, 36, 2793 ± 2794.
[7] M. Sollogoub, J.-M. Mallet, P. SinayÈ, Angew. Chem. 2000, 112, 37 0 ±
372; Angew. Chem. Int. Ed. 2000, 39, 362 ± 364.
[8] W. R. Kobertz, C. R. Bertozzi, M. D. Bednarski, J. Org. Chem. 1996,
61, 1894 ± 1897.
[9] H. Hashimoto, K. Asano, F. Fuji, J. Yoshimura, Carbohydr. Res. 1982,
104, 87± 104.
[10] K. Tatsuta, Y. Niwata, K. Umezawa, K. Toshima, M. Nakata, J.
Antibiot. 1991, 44, 456 ± 458.
[11] B. Casu, M. Petitou, M. Provasoli, P. SinayÈ, Trends Biochem. Sci. 1988,
13, 221 ± 225.
Scheme 5. a) PCC (3 equiv), dry CH2Cl2, 08C, 2 h; b) Tebbe reagent
(2 equiv), Py/THF (1/1), À788C to RT, 20 min; c) 1) BH3 ´ THF (2 equiv),
THF, RT, 1 h; 2) aq. NaOH (11%), aq. H2O2 (35%), 08C to RT, 2 h; d) H2,
Pd/C, EtOAc, MeOH, RT, 2 h.
ido isomer 18 is more complex and
corresponds to the well known
flexibility of idopyranosides.[11]
The two deprotected cyclooc-
tanic sugar mimetics 3 and 19 were
quantitatively obtained after cata-
lytic hydrogenolysis of compounds
17 and 18 (Schemes 5 and 7),
respectively. Compounds 3 and 19
Scheme 6. The boat ± chair
conformation assigned to
compound 17.
Angew. Chem. Int. Ed. 2000, 39, No. 14
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