ORGANIC
LETTERS
2001
Vol. 3, No. 4
607-610
Stereocontrolled Synthesis of
2,3-Anhydro-â-D-lyxofuranosyl
Glycosides
Rajendrakumar Reddy Gadikota, Christopher S. Callam, and Todd L. Lowary*
Department of Chemistry, The Ohio State UniVersity, 100 West 18th AVenue,
Columbus, Ohio 43210
Received December 16, 2000
ABSTRACT
The stereocontrolled synthesis of 2,3-anhydro-â-D-lyxofuranosyl glycosides from thioglycoside 2 and glycosyl sulfoxide 3 is reported.
The key role of oligosaccharide-mediated recognition events
in many important biological events is now undisputed.1 As
interest in the biology and biochemistry of these molecules
has increased, so to has the need for efficient and stereo-
selective methods for the formation of glycosidic bonds.2
bonds,3-5 many either suffer from a lack of generality or
require multiple steps. Accordingly, there is a continuing
need for investigations directed toward the efficient prepara-
tion of glycosidic bonds with this stereochemistry.
Recently, we reported the synthesis of arabinofuranosyl
oligosaccharides that are fragments of two mycobacterial cell
wall polysaccharides.4b,6 One of the targets we synthesized4b
is hexasaccharide 1, which contains two â-D-arabinofuranosyl
linkages (Figure 1). The key step in our synthesis of 1 was
Although some glycosidic linkages can be readily con-
structed in a stereocontrolled manner, others remain chal-
lenging synthetic targets. For example, 1,2-trans linkages
can be reliably prepared through the use of glycosyl donors
with participating (e.g., acyl) protecting groups at C-22a-d
or through the Lewis acid-promoted opening of glycal epox-
ides by nucleophiles.2e-g On the other hand, there are fewer
general strategies for the selective formation of 1,2-cis
linkages,2a-d in particular those possessing 1,2-cis-â stereo-
chemistry, e.g., â-mannopyranosides, â-arabinofuranosides,
and â-fructofuranosides. While some methods have been
developed for the stereoselective synthesis of these glycosidic
(3) â-Mannopyranosides: (a) Ohtake, H.; Ichiba, N.; Ikegami, S. J. Org.
Chem. 2000, 65, 8171. (b) Crich, D.; Sun, S. J. Am. Chem. Soc. 1998, 120,
435. (c) Crich, D.; Sun, S. J. Org. Chem. 1997, 62, 1198. (d) Hodosi, G.;
Kova´c, P. J. Am. Chem. Soc. 1997, 119, 2335. (e) Barresi, F.; Hindsgaul,
O. Front. Nat. Prod. Res. 1996, 1, 1251. (f) Ito Y.; Ogawa, T. Angew.
Chem., Int. Ed. Engl. 1994, 33, 1765. (g) Stork, G.; Kim, G. J. Am. Chem.
Soc. 1992, 114, 1087.
(4) â-Arabinofuranosides: (a) Sanchez, S.; Bamhaoud, T.; Prandi, J.
Tetrahedron Lett. 2000, 41, 7447. (b) D’Souza, F. W.; Lowary, T. L. Org.
Lett. 2000, 2, 1493. (c) Subramaniam, V.; Lowary, T. L. Tetrahedron 1999,
55, 5965. (d) De´sire´, J.; Prandi, J. Carbohydr. Res. 1999, 317, 110. (e)
Mereyala, H. B.; Hotha, S.; Gurjar, M. K. J. Chem. Soc., Chem. Commun.
1997, 685.
(1) (a) Varki, A. Essent. Glycobiol. 1999, 57. (b) Dwek, R. A. Chem.
ReV. 1996, 96, 683.
(5) â-Fructofuranosides: (a) Oscarson, S.; Sehgelmeble F. W. J. Am.
Chem. Soc. 2000, 122, 8869. (b) Krog-Jensen, C.; Oscarson, S. J. Org.
Chem. 1998, 63, 1780. (c) Mu¨ller, T.; Schneider, R.; Schmidt, R. R.
Tetrahedron Lett. 1994, 35, 4763.
(6) (a) D’Souza, F. W.; Ayers, J. D.; McCarren, P. R.; Lowary, T. L. J.
Am. Chem. Soc. 2000, 122, 1251. (b) D’Souza, F. W.; Cheshev, P. E.; Ayers,
J. D.; Lowary, T. L. J. Org. Chem. 1998, 63, 9037. (c) Ayers, J. D.; Lowary,
T. L.; Morehouse, C. B.; Besra, G. S. Bioorg. Med. Chem. Lett. 1998, 8,
437.
(2) Reviews: (a) Davis, B. G. J. Chem. Soc., Perkin Trans. 1 2000, 2137.
(b) Boons, G.-J. Tetrahedron 1996, 52, 1095. (c) Toshima, K.; Tatsuta, K.
Chem. ReV. 1993, 93, 1503. (d) Schmidt, R. R.; Kinzy, W. AdV. Carbohydr.
Chem. Biochem. 1994, 50, 21. (e) Danishefsky, S. J.; Bilodeau, M. T. Angew.
Chem., Int. Ed. Engl. 1996, 35, 1380. (f) Di Bussolo, V.; Kim, Y.-J.; Gin,
D. Y. J. Am. Chem. Soc. 1998, 120, 13515. (g) Kim, Y.-J.; Di Bussolo, V.;
Gin, D. Y. Org. Lett. 2001, 3, 303.
10.1021/ol007008y CCC: $20.00 © 2001 American Chemical Society
Published on Web 01/27/2001