Glucopyranosyl chloride reaction with

C-Glucosidation. Reaction of the protected a-D-glucopyranosyl chloride 1 with silyl enol ethers activated with AgOTf results in a-C-glucosyl esters or ketones. 

In 1879, Michael14 reported that phenyl /3-D-glucopyranoside (3) is obtained by the reaction of tetra-O-acetyl-a-D-glucopyranosyl chloride (1) with potassium phenoxide in aqueous solution. Under the reaction... 

Glycosidation. The silver imidazolate-HgCl2 system favors formation of a-glucosides from reaction of 2,3,4,6-tetra-O-benzyl-a-D-glucopyranosyl chlorides and -a-D-gallactopyranosyl chlorides with sterically hindered alcohols. Addition of tetra-u-bulylammonium chloride (1.4 equiv.) enhances the rate.1... 

The reaction of /l-n-glucopyranosyl-.S -chloroisothiocarbamoyl chloride 135 with 1,3-diarylthioureas 136 affords 3,5-diimino derivatives of 4-aryl-l,2,4-dithiazolidine 137 (Equation 20) <2004JIC155, 2004MI305>. The similar structures 138 <2004MI255, 2005MI495> and 139 <2005MI495> were synthesized in the same manner. 

In 1945, Hurd and Bonner129 130 reported the reaction of either tetra-O-acetyl-a-D-glucopyranosyl chloride or penta-0-acetyl-/3-D-glucopy-ranose with benzene in the presence of aluminum chloride, to form 1,2-/rans-/3-D-glucopyranosylbenzene. The implication of the above results (on /3-D-glucoside formation) in connection with the nature of this latter reaction is obvious. 

Glucosidation.1 Glucosides can be prepared in 50-80% yield by reaction of 3,4,6-tri-O-acetyl-p-D-glucopyranosyl chloride with a primary or secondary alcohol in TMU as solvent and in the presence of 4-A molecular sieves at a temperature pf 110-120° with continuous removal of water from the reaction. Under these conditions, a- and 0-glucosides are formed in about equal amounts. 

In a study of the reaction of the anomeric forms of penta-O-acetyl-D-glucopyranose with titanium chloride in chloroform solution, Lemieux and Brice have found that, at 40°, the a-D anomer reacts but slowly, whereas the /3-d anomer reacts extremely rapidly, with the initial formation of (unstable) tetra-0-acetyl- S-D-glucopyranosyl chloride which then rearranges relatively slowly to (stable) tetra-O-acetyl-a-D-glucopyranosyl chloride. 

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