
TY  - JOUR
A1  - Skelton, Brian W. 
A1  - Stick, Robert V. 
A1  - Stubbs, Keith A. 
A1  - Watts, Andrew G. 
A1  - White, Allan H. 
T1  - The Fluorination (at C5) of Some Derivatives of <emph type="6">D</emph>-Glucose
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 2004
VL  - 57
IS  - 4
SP  - 345
EP  - 353
KW  - carbohydrates &#8212; fluorinated substituents &#8212; fluorination &#8212; photobromination &#8212; synthesis (org.)
UR  - https://doi.org/10.1071/CH03288 
N2  - The photobromination of various per-esters of &#946;-D-glucopyranose and &#945;- and &#946;-D-glucopyranosyl fluoride has yielded 5-bromo derivatives capable of conversion into the corresponding 5-fluorides. The best reagent for this conversion was found to be silver tetrafluoroborate in ether&sol;dichloromethane. The single-crystal X-ray structure determination of penta-O-benzoyl-5-fluoro-&#945;-L-idopyranose is presented.As well, various approaches to 5-fluoro glycopyranosides have been developed. The photobromination of phenyl tetra-O-acetyl-&#946;-D-glucopyranoside, followed by fluorination and protecting group removal gave phenyl 5-fluoro-&#946;-D-glucopyranoside. The photobromination of penta-O-acetyl-&#946;-D-glucopyranose, followed by hydro- lysis and treatment with methanol, gave a hemiacetal that was converted via treatment with diethylaminosulfur trifluoride followed by protecting group removal into methyl 5-fluoro-&#946;-D-glucopyranoside. Methyl 2,3,4-tri-O-benzyl-6-deoxy-&#945;- and -&#946;-D-xylo-hex-5-enosides were converted into their corresponding epoxides with either dimethyldioxirane or 3-chloroperbenzoic acid&semi; subsequent treatment with hydrogen fluoride&sol;pyridine then generated the 5-fluoro glycopyranosides as the major products. A single-crystal X-ray structure determination of 1,6-anhydro-2,3,4-tri-O-benzyl-5-hydroxy-&#946;-L-idose is presented. 
ER  -

