Glucopyranoside ethyl 1-thio

O-Benzylidene Acetals of Methyl a-o-Glucopyranoside, Ethyl 1-Thio-P-o-gluco- and Galactopyranoside... 

Ethyl 1-thio-p-o-glucopyranoside 4-(a-D-Ribofuranosylthio)benzoic acid... 

Growth substrate Maltose (mM) Methyl a-D-glucopyranoside (mM) Ethyl 1-thio-a-D-glucopyranoside (mM) References Comments... 

P. I. Garegg, L. Olsson, and S. Oscarson, Synthesis of methyl(ethyl 2-0-acyl-3,4-di-0-benzyl-l-thio-/ -D-glucopyranosid)uronates and evaluation of their use as reactive / -selective glucuronic acid donors,./. Org. Chem., 60 (1995) 2200-2204. 

Mercaptolysis of /3-D-glucopyranose pentaacetate in ethyl mercaptan at 0°, with zinc chloride as catalyst, gives ethyl tetra-O-acetyl-l-deoxy-1-thio-/S-D-glucopyranoside in 71% yield. Under the same conditions, a-D-glucopyranose pentaacetate reacted only very slowly, but it could be shown that the deoxy-thio-/3-D-glucoside is formed in much greater amount than is the a anomer. Mercaptolysis of the D-mannopyranose pentaacetates under the same conditions for 48 hours resulted in a 70% yield of ethyl tetra-O-acetyl-l-deoxy-l-thio-a-D-mannopyranoside from the /3-D-pentaacetate, and in a 60% yield from the a anomer.103 Inspection, by preparative paper chromatography, of the residual sirups, after deacetylation, led in each case to the isolation of the anomeric ethyl-1-... 

Fig. 27.—Benzylation of the dibutylstannylene acetal of the n iis-l,2-diol in ethyl 4,6-0-benzylidene-l-thio-/3-D-glucopyranoside.135136...

In an investigation of the hydrolysis of ethyl 1-thio-a-n-glucopyranoside, Pacsu and Wilson found that rotational change could not be used to determine the hydrolysis rate-constant, because, in addition to D-glucose, ethyl S-D-glucofuranoside and ethyl a-o-glucopyranoside are formed. 

Ethyl 1-thio-a-D-arabinofuranoside has been synthesized by stereospecific attack of ethanethiolate ion on 3,5-di-0-benzoyl-a,/3-D-arabino-furanosyl chloride. The a-n-glycosyl chloride derivative 1,2-trans) presumably reacts by a two-stage process, with initial attack by the 2-substituent (free hydroxyl) by way of a 1,2-epoxide intermediate, whereas the j9-d anomer (1,2-m) reacts by direct displacement. This behavior resembles that of analogous aldosyl fluoride derivatives with methoxide ion. The 1,2-epoxide derivative 3,4,6-tri-O-acetyl-l,2-anhydro-a-D-glucopjTanose (Brigl s anhydride) reacts with ethanethiol in the presence of zinc chloride to give ethyl 3,4,6-tri-0-acetyl-l-thio- 8-D-glucopyranoside. ... 

---