9,10,11,13-tetra-O-acetyl-8,12-anhydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-glycero-D-gulo-D-galacto-trideco-1,5-pyranose | 130168-52-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 9,10,11,13-tetra-O-acetyl-8,12-anhydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-glycero-D-gulo-D-galacto-trideco-1,5-pyranose
• 英文别名: [(2R,3R,4R,5S,6S)-3,4,5-triacetyloxy-6-[2-[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]ethyl]oxan-2-yl]methyl acetate
• CAS: 130168-52-4
• 化学式: C₂₇H₄₀O₁₄
• 分子量: 588.606
• InChiKey: VVFMZLOJZLFDAQ-ALTCJSSESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.29
• 重原子数：
  41.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  160.58
• 氢给体数：
  0.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  9,10,11,13-tetra-O-acetyl-8,12-anhydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-glycero-D-gulo-D-galacto-trideco-1,5-pyranose 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 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 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：

  2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl(nitro)methane 在 吡啶 、 potassium fluoride 、 sodium tetrahydroborate 、 18-冠醚-6 、 偶氮二异丁腈 、 三正丁基氢锡 、 乙酸酐 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 乙腈 为溶剂， 反应 51.5h， 生成 9,10,11,13-tetra-O-acetyl-8,12-anhydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-glycero-D-gulo-D-galacto-trideco-1,5-pyranose
  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

文献信息

• A concise approach to .beta.-(1.fwdarw.6)- and .beta.,.beta.-(1.fwdarw.1)-linked C-disaccharides. The synthesis of C-.beta.,.beta.-trehalose peracetate
  作者：Olivier R. Martin、Wen Lai

  DOI：10.1021/jo00305a004

  日期：1990.8
• Synthesis of CH₂-Linked α(1,6)-Disaccharide Analogues by α-Selective Radical Coupling <i>C</i>-Glycosylation
  作者：Noriaki Kiya、Yu Hidaka、Kazuteru Usui、Go Hirai

  DOI：10.1021/acs.orglett.9b00133

  日期：2019.3.15

  C-Linked carbohydrate structure, in which the cleavable O-glycosidic linkage is replaced by a carbon unit, is a useful tool for functional analyses of glycoconjugates. We describe a synthetic method for alpha-CH2-linked disaccharide structures, such as Glc(1,6)-Glc, by stereoselective radical-coupling C-glycosylation between a conformationally constrained and stable C1-sp(3) hybridized xanthate donor and a carefully designed acceptor.