(2R,3S,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol | 197230-25-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol
• CAS: 197230-25-4
• 化学式: C₁₉H₃₂O₁₀
• 分子量: 420.457
• InChiKey: XMDXGXDFADEHMM-REAUDJNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.99
• 重原子数：
  29.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  136.3
• 氢给体数：
  4.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol 在 Amberlite IR-120(H+) ion-exchange resin 作用下， 以 水 为溶剂， 反应 2.5h， 生成 8,12-anhydro-6,7-dideoxy-D-glycero-D-gulo-D-galacto-tridecose
  参考文献：
  名称：

  Synthesis and conformational studies of .beta.-(1.fwdarw.6)- and .beta.,.beta.-(1.fwdarw.1)-linked C-disaccharides

  摘要：

  An expeditious methodology for the synthesis of beta-(1-->6)- and beta,beta-(1-->1)-linked C-disaccharides has been developed. The methodology is based on the fluoride ion-mediated coupling of the (base-stable) nitronate anion derived from a glycosylnitromethane (1) and an aldehydo-hexodialdose or -hexose derivative. The carba-analogs (methylene-bridged analogs) of beta-D-Glc-(1-->6)-D-Gal and of beta,beta-trehalose (beta-D-Glc-(1-->1)-beta-D-Glc) were thus obtained in six steps only from 1 and D-galactose-derived aldehyde 4 or aldehydo-D-glucose derivative 12, respectively. The preferred conformation of the (1-->1)-linked C-disaccharides, including the symmetrical C-beta,beta-trehalose, was established on the basis of the vicinal coupling constants about the interglycosidic C-C linkages. In all the compounds of this series, the beta-C-glycosidic linkages were found to adopt preferentially the ''anti'' conformation (C2-C1-C7-C1' torsional angle = approximately 180-degrees). Our studies revealed, in particular, that the solution conformation of C-beta,beta-trehalose, in which no stereoelectronic (exo-anomeric) effects are operating, is the same as the one predicted and determined for beta,beta-trehalose, thereby demonstrating that steric effects alone are sufficient to cause the greater stability of the preferred conformation of the parent disaccharide.

  DOI：

  10.1021/jo00053a033
• 作为产物：
  描述：

  6-deoxy-1,2:3,4-di-O-isopropylidene-6-(triphenylphosphino)-α-D-galactopyranose iodide 在 palladium dihydroxide 六甲基磷酰三胺 、 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 乙酸乙酯 为溶剂， -30.0~25.0 ℃ 、303.98 kPa 条件下， 反应 7.0h， 生成 (2R,3S,4R,5R,6S)-2-Hydroxymethyl-6-[2-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-ethyl]-tetrahydro-pyran-3,4,5-triol
  参考文献：
  名称：

  Synthesis of α- and β-d-(1→6)-C-Disaccharides by Wittig Olefination of Formyl C-Glycosides with Glycopyranose 6-Phosphoranes

  摘要：

  The synthesis of (1-->6)-C-disaccharides by Wittig condensation of formyl C-glycofuranosides and pyranosides with galacto-and glucopyranose B-phosphoranes is described herein. The method involves the coupling of the sugar aldehydes with the ylides and the reduction of the double bond of the resulting sugar alkenes, in most of the cases by catalytic hydrogenation. The reduction with nickel boride or diimide is employed in some special cases. O-Benzyl protective groups are removed by catalytic hydrogenation either in the course of the reduction of the double bond or in a subsequent step, while O-isopropylidene groups are cleaved by treatment with Amberlite IR-120. In this way, eight free beta-D-(1-->6)-C-disaccharides have been prepared in 26-61% overall yield starting from B-linked formyl C-glycosides. These include C-linked analogues of the biologically active disaccharides allolactose (Gal beta 1,6Glc), gentiobiose (Glc beta 1,6Glc), and N-acetylamino disaccharides (GalNHAc beta,6Gal and GalNHAc beta 1,6Glc). Moreover, the synthesis of two alpha-D-(1-->6)-C-disaccharides is described from formyl C-furanosides. The limiting condition of the synthesis of these stereoisomers is the configurational instability of the alpha-linked formyl C-glycosides under the basic conditions of the Wittig olefination.

  DOI：

  10.1021/jo971177n