
TY  - JOUR
A1  - Patroni, JJ 
A1  - Skelton, BW 
A1  - Stick, RV 
A1  - White, RV 
T1  - The reaction of methyl 4,6-O-isopropylidene-2,3-O-thiocarbonyl-&#945;-D-mannoside with methyl iodide : a synthesis of methyl &#945;-Tyveloside (methyl 3,6-dideoxy-&#945;-D-<I>arabino</I>-hexopyranoside)
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1980
VL  - 33
IS  - 5
SP  - 987
EP  - 999
KW  - 
UR  - https://doi.org/10.1071/CH9800987 
N2  - The reaction of methyl 4,6-O-isopropylidene-2,3-O-thiocarbonyl-&#945;-D- mannoside with methyl iodide gives two major products, methyl 3,6- dideoxy-3,6-diiodo-2-O-(methylthio)carbonyl-&#945;-D-altro-pyranoside and methyl 2,3-O-carbonyl-6-deoxy-6-iodo-&#945;-D-mannopyranoside, both of which lack the 4,6-O-isopropylidene grouping but contain the 6-deoxy-6-iodo function, and another minor product. One of the major products, methyl 3,6-dideoxy-3,6-diiodo-2-O-(methylthio)carbonyl-&#945;-D-altro-pyranoside, is converted into methyl &#945;-tyveloside by sequential reduction and ester removal. The incorporation of iodine at C6 is seemingly due to hydrogen iodide, and may be suppressed in the presence of N,N,N,N- tetramethylnaphthalene-1,8-diamine or propylene oxide, or by the use of 4,6-O-benzylidene-2,3-O-thiocarbonyl-&#945;-D-mannoside as substrate. Methyl iodide/propylene oxide is apparently an efficient combination for thiocarbonate (C=S) into carbonate conversion. The structure of the minor product was shown by single-crystal X-ray diffraction to be 1,6- anhydro-3-deoxy-3-iodo-2-O-(methylthio)carbonyl-&#946;-D-altropyranose. 
ER  -

