糖二甲基硫代氨基甲酸盐的光化学转化为脱氧糖。

Photochemical conversion of sugar dimethylthiocarbamates into deoxy sugars.

作者信息

Bell H, Horton D, Williams D M, Winter-Mihaly E

出版信息

Carbohydr Res. 1977 Sep;58(1):109-24. doi: 10.1016/s0008-6215(00)83408-4.

Abstract

Protected sugar derivatives having one free hydroxyl group may be deoxygenated at the alcoholic position by ultraviolet irradiation of the corresponding dimethylthiocarbamic esters; a concomitant process leads also to the original alcohol. Thus, on photolysis, the 6-dimethylthiocarbamate (1) of 1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (3) gives 6-deoxy-1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (2) together with 3. Likewise, the 4-dimethylthiocarbamate (6) of 1,6-anhydro-2,3-O-isopropylidene-beta-D-mannopyranose (8) gives a mixture of the 4-deoxy derivative 7 and the alcohol 8. 3-Deoxy-1,2:5,6-di-O-isopropylidene-alpha-D-ribo-hexofuranose (10) was obtained by irradiation of 3-O-(dimethylthiocarbamoyl)-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (9), and was accompanied by 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (11). The 3-deoxy-3-iodo analog (14) of 11 underwent conversion into 10 by photolysis, and the deoxy sugar 10 was also prepared from 3,3'-dithiobis(1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose) (12) by the action of Raney nickel. Photolysis of the 2-dimethylthiocarbamate (16) of methyl 3,4-O-isopropylidene-beta-L-arabinopyranoside (18 gave the 2-deoxy derivative (17), together with the parent alcohol 18, and the same pair of products was obtained by the action of tributylstannane on the 2-(methylthio)thiocarbonyl derivative (19) of 18, although the dimethylthiocarbamate 16 was unreactive toward tributylstannane.

摘要

具有一个游离羟基的被保护糖衍生物可通过对相应的二甲基硫代氨基甲酸酯进行紫外线照射，在醇羟基位置脱氧；一个伴随过程也会生成原来的醇。因此，在光解时，1,2:3,4-二-O-异亚丙基-α-D-吡喃半乳糖（3）的6-二甲基硫代氨基甲酸酯（1）生成6-脱氧-1,2:3,4-二-O-异亚丙基-α-D-吡喃半乳糖（2）以及3。同样，1,6-脱水-2,3-O-异亚丙基-β-D-甘露吡喃糖（8）的4-二甲基硫代氨基甲酸酯（6）生成4-脱氧衍生物7和醇8的混合物。通过对3-O-（二甲基硫代氨基甲酰基）-1,2:5,6-二-O-异亚丙基-α-D-呋喃葡萄糖（9）进行照射得到3-脱氧-1,2:5,6-二-O-异亚丙基-α-D-核糖己呋喃糖（10），同时伴有1,2:5,6-二-O-异亚丙基-α-D-呋喃葡萄糖（11）。11的3-脱氧-3-碘类似物（14）通过光解转化为10，脱氧糖10也可由3,3'-二硫代双（1,2:5,6-二-O-异亚丙基-α-D-呋喃葡萄糖）（12）在雷尼镍作用下制备。甲基3,4-O-异亚丙基-β-L-阿拉伯吡喃糖苷（18）的2-二甲基硫代氨基甲酸酯（16）光解生成2-脱氧衍生物（17）以及母体醇18，并且通过三丁基锡对18的2-（甲硫基）硫代羰基衍生物（19）的作用也得到相同的一对产物，尽管二甲基硫代氨基甲酸酯16对三丁基锡无反应。