King-Morris M J, Bondo P B, Mrowca R A, Serianni A S
Omicron Biochemicals, Inc., Ithaca, New York 14850.
Carbohydr Res. 1988 Apr 1;175(1):49-58. doi: 10.1016/0008-6215(88)80155-1.
1,2-O-Isopropylidene-alpha-D-xylo-pentodialdo-1,4-furanose (1) has been used as the parent aldose in the preparation of D-(6-13C)glucose and L-6-13C)idose via cyanohydrin reduction. The addition of K13CN (pH 6.8, 5 min) to 1 yields D-gluco and L-ido cyanohydrins that are readily reduced with H2 and Pd-BaSO4, to give 1,2-O-isopropylidene-alpha-D-gluco-hexodialdo-1,4-furanose (2; approximately 65%) and 1,2-O-isopropylidene-beta-L-ido-hexodialdo-1,4-furanose (3; 35%). Aldehydes 2 and 3 are reduced in situ with NaBH4, the resulting alcohols are deprotected with aqueous acid, and the aldoses are chromatographed on Dowex 50 X-8 (Ca2+) ion-exchange resin (200-400 mesh), to yield D-(6-13C)glucose (6) and L-(6-13C)idose (7). Molybdate epimerization of 6 and 7 yields D-(6-13C)mannose and L-(6-13C)gulose, respectively. A similar reaction scheme may be applied to methyl 2,3-O-isopropylidene-beta-D-ribo-pentodialdo-1,4-furanoside to generate the remaining four (6-13C)aldohexoses. This route is considerably simpler than the traditional Kiliani-Fischer route, and higher yields are obtained.
1,2 - O - 异亚丙基 - α - D - 木糖 - 1,4 - 呋喃戊二醛（1）已被用作母体醛糖，通过氰醇还原法制备D -（6 - ¹³C）葡萄糖和L -（6 - ¹³C）艾杜糖。向1中加入K¹³CN（pH 6.8，5分钟），得到D - 葡萄糖和L - 艾杜糖氰醇，它们很容易用H₂和Pd - BaSO₄还原，得到1,2 - O - 异亚丙基 - α - D - 葡萄糖 - 1,4 - 呋喃己二醛（2；约65%）和1,2 - O - 异亚丙基 - β - L - 艾杜糖 - 1,4 - 呋喃己二醛（3；35%）。醛2和3用NaBH₄原位还原，所得醇用酸水溶液脱保护，醛糖在Dowex 50 X - 8（Ca²⁺）离子交换树脂（200 - 400目）上进行色谱分离，得到D -（6 - ¹³C）葡萄糖（6）和L -（6 - ¹³C）艾杜糖（7）。6和7的钼酸差向异构化分别得到D -（6 - ¹³C）甘露糖和L -（6 - ¹³C）古洛糖。类似的反应方案可应用于2,3 - O - 异亚丙基 - β - D - 核糖 - 1,4 - 呋喃戊二醛甲酯，以生成其余四种（6 - ¹³C）醛己糖。该路线比传统的基利安尼 - 费歇尔路线要简单得多，并且产率更高。
