Myers R W, Lee Y C
Carbohydr Res. 1986 Sep 1;152:143-58. doi: 10.1016/s0008-6215(00)90295-7.
3,7-Anhydro-1-deoxy-1-diazo-D-glycero-L-manno-2-octulose (6a; diazomethyl beta-D-galactopyranosyl ketone) and 3,7-anhydro-1-deoxy-1-diazo-D-glycero-D-gulo-2-octulose (6b; diazomethyl beta-D-glucopyranosyl ketone) have been prepared. Readily available C-glycosyl compounds possessing the appropriate stereo-chemistry and hydroxyl-group protection, viz., per-O-acetyl-2,6-anhydroheptononitriles and per-O-acetyl-2,6-anhydroheptonamides, were employed as precursors to per-O-acetyl-2,6-anhydroheptonic acids. These key intermediates were then converted into mixed carboxylic-carbonic acid anhydrides, and these caused to react with diazomethane, to give the corresponding per-O-acetyl-3,7-anhydro-1-deoxy-1-diazo-2-octuloses. Zemplén deacetylation gave, stereospecifically, the crystalline target-molecules in good overall yield. It is proposed that such C-glycosyl compounds as 6a and 6b, which possess the diazoacetyl functional groups as their "aglycon", will be useful as enzyme-activated irreversible inhibitors (suicide substrates) of glycosidases, and as photoaffinity-labeling reagents and classical affinity-labeling reagents for carbohydrate-binding proteins.
已制备出3,7-脱水-1-脱氧-1-重氮-D-甘油-L-甘露-2-辛酮糖（6a；重氮甲基β-D-吡喃半乳糖基酮）和3,7-脱水-1-脱氧-1-重氮-D-甘油-D-古洛-2-辛酮糖（6b；重氮甲基β-D-吡喃葡萄糖基酮）。具有适当立体化学和羟基保护的易于获得的C-糖苷化合物，即全-O-乙酰基-2,6-脱水庚腈和全-O-乙酰基-2,6-脱水庚酰胺，被用作全-O-乙酰基-2,6-脱水庚酸的前体。然后将这些关键中间体转化为混合的羧酸-碳酸酐，并使其与重氮甲烷反应，得到相应的全-O-乙酰基-3,7-脱水-1-脱氧-1-重氮-2-辛酮糖。通过泽普林脱乙酰化反应，立体专一性地以良好的总收率得到了结晶的目标分子。有人提出，像6a和6b这样具有重氮乙酰官能团作为其“苷元”的C-糖苷化合物，将可用作糖苷酶的酶激活不可逆抑制剂（自杀底物），以及用作碳水化合物结合蛋白的光亲和标记试剂和经典亲和标记试剂。
