Baer H H, Hernández Mateo F
Ottawa-Carleton Institute for Research and Graduate Studies in Chemistry, Department of Chemistry, University of Ottawa, Ontario, Canada.
Carbohydr Res. 1988 Dec 31;184:151-61. doi: 10.1016/0008-6215(88)80013-2.
Two new trideoxyglycosides, methyl 3,4,6-trideoxy-3-nitro-alpha-L-lyxo-hexopyranoside (7) and its alpha-L-arabino isomer, as well as the known alpha-L-xylo isomer (15), were synthesized from methyl 3,6-dideoxy-3-nitro-alpha-L-glucopyranoside (1) by methods involving elimination and reduction processes in mesylates prepared from 1. Catalytic hydrogenation of 7 and 15 gave the new and the known aminodeoxyglycosides, respectively, both of which were N-(trifluoroacetyl)ated and sub-subsequently O-(trifluoromethylsulfonyl)ated. Various attempts to effect displacement by fluoride ion in the N-protected 2-triflates so obtained, and also in a related 3-azido-2-triflate, were unsuccessful as far as fluorination at C-2 was concerned. Among other products, two new 2-enopyranosides resulting from elimination of triflic acid were obtained.
从3,6-二脱氧-3-硝基-α-L-吡喃葡萄糖苷（1）出发，通过涉及由1制备的甲磺酸酯的消除和还原过程的方法，合成了两种新的三脱氧糖苷，3,4,6-三脱氧-3-硝基-α-L-吡喃来苏糖甲基苷（7）及其α-L-阿拉伯糖异构体，以及已知的α-L-木糖异构体（15）。7和15的催化氢化分别得到了新的和已知的氨基脱氧糖苷，二者均进行了N-（三氟乙酰基）化，随后进行了O-（三氟甲基磺酰基）化。就C-2处的氟化而言，尝试用氟离子取代如此得到的N-保护的2-三氟甲磺酸酯以及相关的3-叠氮基-2-三氟甲磺酸酯中的氟均未成功。在其他产物中，得到了两种由三氟甲磺酸消除产生的新的2-烯吡喃糖苷。
