Baer H H, Breton R L, Shen Y P
Department of Chemistry, University of Ottawa, Ontario, Canada.
Carbohydr Res. 1990 Apr 25;200:377-89. doi: 10.1016/0008-6215(90)84204-8.
Crystalline 6-deoxy-alpha-D-gluco-heptopyranosyl 6-deoxy-alpha-D-gluco- heptopyranoside (8) and (6-deoxy-alpha-D-gluco-heptopyranosyluronic acid) 6-deoxy-alpha-D-gluco-heptopyranosiduronic acid (7) were synthesized from alpha, alpha-trehalose (1). Reaction of 2,3,4,2',3',4'-hexa-O-acetyl- 6,6'-di-O-tosyl-alpha, alpha-trehalose with sodium dicarbonylcyclopentadienyliron, followed by oxidative hydrolysis or methanolysis, gave the 2,3,4,2',3',4'-hexa-acetate of 7 or its dimethyl ester, respectively. O-Deacetylation (Zemplén) then gave 7 and its dimethyl ester. Reduction of the hexa-O-acetyldicarboxylic acid with borane-oxolane complex yielded 8. Alternatively, cyanide displacement of hexa-O-acetyl-alpha, alpha-trehalose 6,6'-ditriflate gave the dinitrile hexa-acetate of 7, which was O-deacetylated and then hydrolyzed with alkaline hydrogen peroxide to yield 7. 2,3,4,2',3',4'-Hexa-O-benzyl-alpha, alpha-trehalose 6,6'-ditriflate was similarly converted into the dinitrile, which was hydrolyzed to the corresponding diamide. Treatment of the 2,3,4,2',3',4'-hexa- O-acetyl-alpha, alpha-trehalosuronic acid 16 with thionyl chloride followed by diazomethane gave a crystalline bisdiazoketone which, however, failed to produce the expected bis(heptosiduronic acid) on attempted Wolff rearrangement.
结晶状的6 - 脱氧 - α - D - 吡喃葡庚糖基6 - 脱氧 - α - D - 吡喃葡庚糖苷（8）和（6 - 脱氧 - α - D - 吡喃葡庚糖醛酸基）6 - 脱氧 - α - D - 吡喃葡庚糖醛酸苷（7）由α，α - 海藻糖（1）合成。2,3,4,2',3',4'-六 - O - 乙酰基 - 6,6'-二 - O - 甲苯磺酰基 - α，α - 海藻糖与二羰基环戊二烯基铁钠反应，随后进行氧化水解或甲醇解，分别得到7的2,3,4,2',3',4'-六乙酸酯或其二甲酯。然后进行O - 脱乙酰化反应（泽普林反应）得到7及其二甲酯。用硼烷 - 氧杂环戊烷络合物还原六 - O - 乙酰基二羧酸得到8。另外，六 - O - 乙酰基 - α，α - 海藻糖6,6'-二磺酸酯的氰化物取代反应得到7的二腈六乙酸酯，将其进行O - 脱乙酰化，然后用碱性过氧化氢水解得到7。2,3,4,2',3',4'-六 - O - 苄基 - α，α - 海藻糖6,6'-二磺酸酯以类似方式转化为二腈，再水解为相应的二酰胺。用亚硫酰氯处理2,3,4,2',3',4'-六 - O - 乙酰基 - α，α - 海藻糖醛酸16，随后用重氮甲烷处理得到一种结晶状双重氮酮，然而，在尝试进行沃尔夫重排时未能生成预期的双（庚糖醛酸）。
