Jain R K, Dubey R, Abbas S A, Matta K L
Carbohydr Res. 1987 Mar 15;161(1):31-7. doi: 10.1016/0008-6215(87)84003-x.
Treatment of methyl 3-O-benzyl-2-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-alpha-D- mannopyranoside (1) with tert-butyldiphenylsilyl chloride in N,N-dimethylformamide afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-(2,3,4,6-tetra-O-acetyl -alpha-D- mannopyranosyl)-alpha-D-mannopyranoside (2). Oxidation of 2 with pyridinium chlorochromate, followed by reduction of the carbonyl group, and subsequent O-deacetylation afforded methyl 3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-O-alpha-D-mannopyranosyl- alpha-D- talopyranoside (5). Cleavage of the tert-butyldiphenylsilyl group of 5 with tetrabutylammonium fluoride in oxolane, followed by hydrogenolysis, gave methyl 2-O-alpha-D-mannopyranosyl-alpha-D-talopyranoside (7). O-Deacetylation of 1 gave methyl 3-O-benzyl-2-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside (8). Treatment of 8 with tert-butyldiphenylsilyl chloride afforded a 6,6'-disilyl derivative, which was converted into a 2',3'-O-isopropylidene derivative, and then further oxidized with pyridinium chlorochromate. The resulting diketone was reduced and removal of the protecting groups gave methyl 2-O-alpha-D-talopyranosyl-alpha-D-talopyranoside (15). The structures of both 7 and 15 were established by 13C-n.m.r. spectroscopy.
在N，N-二甲基甲酰胺中，用叔丁基二苯基氯硅烷处理3-O-苄基-2-O-（2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基）-α-D-甘露吡喃糖苷（1），得到3-O-苄基-6-O-叔丁基二苯基硅基-2-O-（2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基）-α-D-甘露吡喃糖苷（2）。用氯铬酸吡啶鎓氧化2，接着还原羰基，随后进行O-脱乙酰化，得到3-O-苄基-6-O-叔丁基二苯基硅基-2-O-α-D-甘露吡喃糖基-α-D-塔罗吡喃糖苷（5）。在四氢呋喃中用四丁基氟化铵裂解5的叔丁基二苯基硅基，接着进行氢解，得到2-O-α-D-甘露吡喃糖基-α-D-塔罗吡喃糖苷（7）。1的O-脱乙酰化得到3-O-苄基-2-O-α-D-甘露吡喃糖基-α-D-甘露吡喃糖苷（8）。用叔丁基二苯基氯硅烷处理8得到一个6,6'-二硅基衍生物，将其转化为2',3'-O-异亚丙基衍生物，然后用氯铬酸吡啶鎓进一步氧化。所得二酮经还原并除去保护基，得到2-O-α-D-塔罗吡喃糖基-α-D-塔罗吡喃糖苷（15）。7和15的结构通过13C-核磁共振光谱确定。
