Synthesis of sulfur-linked analogues of nigerose, laminarabiose, laminaratriose, gentiobiose, gentiotriose, and laminaran trisaccharide Y.
Sulfur-linked analogues of 3-O-alpha-D-glucopyranosyl-D-glucose (nigerose), 3-O-beta-D-glucopyranosyl-D-glucose (laminarabiose), 6-O-beta-D-glucopyranosyl-D-glucose (gentiobiose), O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->3)-D-glucos e (laminaratriose), O-beta-D-glucopyranosyl)-(1-->6)-O-beta-D-glucopyranosyl-(1-->6)-D-gluco se (gentiotriose) and 3,6-di-O-beta-D-glucopyranosyl-D-glucose (laminaran trisaccharide Y), namely, respectively, 3-thionigerose (6), 3-thiolaminarabiose (11), 6-thiogentiobiose (21), 3I,3II-dithiolaminaratriose (16), 6I,6II-dithiogentiotriose (29) and 3I,6I-dithiolaminaran trisaccharide Y (37) have been conveniently prepared by SN2 reactions of the corresponding anomer of D-glucopyranose 1-thiolate with suitably activated monosaccharide derivatives in N,N-dimethylformamide (for 6 and 21) or in tetrahydrofuran in the presence of a crown ether (for 11). A sequence involving the reaction of non-anomeric thiolates with 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl bromide was alternatively used for the preparation of 11 and 21 but proved less satisfactory. The preparation of thiotrisaccharides 16, 29, and 37 involved a mixed approach.
Contour-Galcera
M O
MO
Département de Recherche Fondamentale sur la Matière Condensée/SESAM, CEntre d'Etudes de Grenoble, France.
Guillot
J M
JM
Ortiz-Mellet
C
C
Pflieger-Carrara
F
F
Defaye
J
J
Gelas
J
J
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000138:chemical synthesis / Q000737:chemistry*; D005936:Glucans; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D015394:Molecular Structure; D011134:Polysaccharides / Q000737:chemistry*; D013863:Thioglucosides / Q000737:chemistry*; D014312:Trisaccharides / Q000138:chemical synthesis
D004187:Disaccharides; D005936:Glucans; D011134:Polysaccharides; D013863:Thioglucosides; D014312:Trisaccharides; C014637:laminaribiose; C008247:laminaran; C100052:gentiobiose