20881-04-3Relevant articles and documents
CYCLIC DINUCLEOTIDES AS ANTICANCER AGENTS
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Paragraph 1450; 1451; 1452, (2019/02/13)
The present invention is directed to compounds of the formulae I, II and III as shown below wherein all substituents are defined herein, as well as pharmaceutically acceptable compositions comprising compounds of the invention and methods of using said compositions in the treatment of various disorders.
1,2-Cyclic sulfite and sulfate furanoside diesters: improved syntheses and stability
Hardacre, Christopher,Messina, Ivano,Migaud, Marie E.,Ness, Kerry A.,Norman, Sarah E.
experimental part, p. 6341 - 6347 (2009/12/04)
The facile syntheses of 1,2- and 3,5-cyclic sulfite and sulfate furanoside diesters were conducted in molecular solvents and ionic liquids in the presence of immobilised morpholine. Molecular solvents and ionic liquids performed similarly with regards to overall yields. However, the use of ILs allowed for the reactions to be carried out under atmospheric conditions and showed good recyclability. Additionally, increases in product stability was achieved in ILs over organic solvents, in particular, in bis{(trifluoromethanesulfonyl)imide} and trispentafluoro-ethyltrifluorophosphate-based ionic liquids, which were also excellent media to control the hydrolysis of thionyl chloride and sulfuryl chloride.
An economic synthesis of 1,2,3,4-tetra-O-acetyl-5-thio-D-xylopyranose and its transformation into 4-substituted-phenyl 1,5-dithio-D-xylopyranosides possessing antithrombotic activity
Bozo, Eva,Boros, Sandor,Kuszmann, Janos,Gacs-Baitz, Eszter,Parkanyi, Laszlo
, p. 297 - 310 (2007/10/03)
D-Xylose was converted via 1,2-O-isopropylidene-α-D-xylofuranose (4) into 3-O-benzoyl-5-S-benzoyl- 1,2-O-isopropylidene-α-D-xylofuranose which, after methanolysis, acetylation and subsequent acetolysis afforded 1,2,3,4-tetra-O-acetyl-5-thio-α-D-xylopyranose (14) in an overall yield of 36%. Reaction of 4 with thionyl chloride gave a mixture of the diastereomeric cyclic sulfites, the structures of which were established by X-ray crystallography. Their oxidation with sodium periodate afforded the corresponding cyclic sulfate 23. Treatment of 23 with potassium thioacetate gave the potassium salt of 5-S-acetyl-1,2-O-isopropylidene-α-D-xylofuranose 3-O-sulfonic acid (26) which, after methanolysis, acetylation and subsequent acetolysis afforded 14 in an overall yield of 56%. Treatment of 4 with sulfuryl chloride gave a mixture containing 5-chloro-3-O-chlorosulfonyl-5-deoxy-1, 2-O-isopropylidene-α-D-xylofuranose, 3,7,9,11-tetraoxa-4-thia-10-dimethyl-tricyclo[6,3,0,02,6]undecane S-dioxide and 23 in a 2:3:7 ratio. Tetraacetate 14 was converted into the α-1-bromide 18 as well as into the α-1-O-trichloroacetimidate 17. These three compounds were used as donors for the glycosylation with 4-cyanothiophenol, affording the 4-cyanophenyl 2,3,4-tri-O-acctyl-1,5-dithio-α- (29) and β-D-xylopyranoside (30) in different ratios, depending on the reaction conditions, When donor 18 was used in the presence of potassium carbonate, besides 29 and 30 two aryl C-glycosylated-thioglycosides, i.e. 4-cyano-2-(2, 3,4-tri-O-acetyl-5-thio-β-D- xylopyranosyl)phenyl 2,3,4-tri-O-acetpy-1,5-dithio-α- and β-D-xylopyranoside (32 and 33) as well as 4-cyano-2-(2,3,4-tri-O-acetyl-5-thio-β-D-xylopyranosyl)phenyl disulfide 34 could be isolated as byproducts. Deacetylation of 30 with sodium methoxide in methanol afforded, besides 4-cyanophenyl 1,5-dithio-β-D-xylopyranoside (1), the corresponding 4-[(methoxy)(imino)methyl]phenyl glycoside 2. The 4-cyano group of 1 was converted into the 4-aminothiocarbonyl, the 4-(methylthio)(imino)methyl, the 4-amidino and the 4-(imino)(hydrazino)methyl group. All of these glycosides showed a significant antithrombotic activity on rats.
