1,2-O-<1-(exo-ethoxy)ethylidene>-α-D-glucopyranose | 97673-01-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,2-O-<1-(exo-ethoxy)ethylidene>-α-D-glucopyranose
• 英文别名: 1,2-O-(1-exo-Ethoxyethylidene)-α-D-glucopyranose；(2S,3aR,5R,6S,7S,7aR)-2-ethoxy-5-(hydroxymethyl)-2-methyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-6,7-diol
• CAS: 97673-01-3
• 化学式: C₁₀H₁₈O₇
• 分子量: 250.249
• InChiKey: YLYHVAFCXKLCAL-PXSBVEPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  97.6
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,2-O-<1-(exo-ethoxy)ethylidene>-α-D-glucopyranose 在 barium dihydroxide 、 氯化亚砜 、 cation-exchange resin (H⁺) 、 四丁基溴化铵 、 三丁基氧化锡 、 barium(II) oxide 、 silver(l) oxide 作用下， 以 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 39.25h， 生成 2-O-acetyl-3-O-allyl-4-O-benzyl-6-O-(tert-butyldiphenylsilyl)-D-glucopyranosyl chloride
  参考文献：
  名称：

  适合于合成糖蛋白“核心”寡糖的糖基供体的制备。

  摘要：

  2-O-乙酰基-3-O-烯丙基-4-O-苄基-6-O-叔丁基二苯基甲硅烷基-D-葡萄糖吡喃糖基氯（14），一种适合合成对应于N-糖蛋白糖的寡糖的糖基供体“核心”是由3,4,6-三-O-乙酰基-1,2-O- [1-（外-乙氧基）亚乙基）-α-D-吡喃葡萄糖通过高效的六步路线合成的。由三氟甲磺酸银促进的14与苄基2-乙酰氨基-3,6-二-O-苄基-2-脱氧-α-D-吡喃葡萄糖苷的偶联产生了受保护的与β-D-（1 ---- 4）连接的二糖收率38％，但也发生了主要的副反应。当在偶联反应之前将叔丁基二苯基甲硅烷基从14定量除去后再取代时，糖苷化的产率增加到55％，并且避免了主要副产物。

  DOI：

  10.1016/0008-6215(85)85203-4
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(S)-(1-ethoxyethylidene)-α-D-glucopyranose 在 三乙胺 作用下， 以 甲醇 为溶剂， 以88%的产率得到1,2-O-<1-(exo-ethoxy)ethylidene>-α-D-glucopyranose
  参考文献：
  名称：

  适合于合成糖蛋白“核心”寡糖的糖基供体的制备。

  摘要：

  2-O-乙酰基-3-O-烯丙基-4-O-苄基-6-O-叔丁基二苯基甲硅烷基-D-葡萄糖吡喃糖基氯（14），一种适合合成对应于N-糖蛋白糖的寡糖的糖基供体“核心”是由3,4,6-三-O-乙酰基-1,2-O- [1-（外-乙氧基）亚乙基）-α-D-吡喃葡萄糖通过高效的六步路线合成的。由三氟甲磺酸银促进的14与苄基2-乙酰氨基-3,6-二-O-苄基-2-脱氧-α-D-吡喃葡萄糖苷的偶联产生了受保护的与β-D-（1 ---- 4）连接的二糖收率38％，但也发生了主要的副反应。当在偶联反应之前将叔丁基二苯基甲硅烷基从14定量除去后再取代时，糖苷化的产率增加到55％，并且避免了主要副产物。

  DOI：

  10.1016/0008-6215(85)85203-4

文献信息

• Total Synthesis of Myrmekioside A, a Mono-<i>O</i>-alkyl-diglycosylglycerol from Marine Sponge<i>Myrmekioderma</i>sp.
  作者：Jun Zhang、Chunxia Li、Linlin Sun、Guangli Yu、Huashi Guan

  DOI：10.1002/ejoc.201500471

  日期：2015.7

  Myrmekioside A, which was isolated from the marine sponge Myrmekioderma sp. as a member of the family of natural mono-O-alkyl-diglycosylglycerols, and which has a strong reversion effect on the tumor cell morphology of ras-transformed cells at 5 μg/mL, was synthesized for the first time in 17 steps and 14 % overall yield. The β-glycosidic linkages in myrmekioside A were successfully constructed by

  Myrmekioside A，它是从海洋海绵 Myrmekioderma sp. 中分离出来的。作为天然单-O-烷基-二糖基甘油家族的一员，5 μg/mL对ras转化细胞的肿瘤细胞形态有很强的逆转作用，首次分17步和14步合成% 总产率。myrmekioside A 中的 β-糖苷键是通过使用三氯乙酰亚胺和硫代糖苷作为糖基供体的相邻基团参与方法成功构建的。甘油主链 C-2 处的 2R 绝对构型源自 (S)-1,2- 异丙基甘油 (8)。这种合成方法可能适用于制备其他具有不同糖和烷基链的桃金娘苷类似物，用于进一步的结构-活性关系研究。
• Comparison of Several Glucuronate Glycosyl Donors
  作者：Anahit Pews‐Davtyan、Alexander Pirojan、Izabella Shaljyan、Aida A. Awetissjan、Helmut Reinke、Christian Vogel

  DOI：10.1081/car-120026603

  日期：2003.12.31

  Methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-alpha-D-glucopyranuronate (12), methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-ethoxyethylidene)]-alpha-D-glucopyranuronate (14), methyl 2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranuronate bromide (15), methyl (2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranosyl)uronate trichloroacetimidate (17), and methyl (2,3,4-tri-O-benzyl-alpha/beta-D-glucopyranosyl)uronate trichloroacetimidate (30) were synthesized and used as glycosyl donors. Glycosylation reactions of 12 with (5-R)-2,3,4,5-tetrahydro-5-trityloxymethyl-2-furanone (32) and 14,15,17 with the corresponding (5-R)-2,3,4,5-tetrahydro-5-hydroxymethyl-2-furanone (31) provided the exclusively beta-linked glucuronide 33 in 69%, 28%, 45%, and 71% yield, respectively. The coupling of donor 30 with acceptor 31 furnished the glucuronated lactone 35 in 70% yield with a surprisingly high content (20%) of the undesired alpha-linked sugar residue. The structure of 33 was proved by NMR and X-ray diffraction studies. In a model reaction a complete deprotection procedure of the glucuronic acid lactone conjugation was demonstrated.
• CAPON, BRIAN;LEE, YIU-CHUNG, J. ORG. CHEM., 56,(1991) N4, C. 4428-4435
  作者：CAPON, BRIAN、LEE, YIU-CHUNG

  DOI：——

  日期：——
• An investigation of intermediates in the hydrolysis of ortho esters derived from D-glucose and D-mannose
  作者：Brian Capon、Yiu Chung Lee

  DOI：10.1021/jo00014a018

  日期：1991.7

  The hydrolysis of a series of 1,2-ortho esters derived from alpha-D-glucopyranose and beta-D-mannopyranose have been investigated by NMR and UV spectroscopy. When the hydrolysis of 1,2-O-(1-exo-ethoxyethylidene)-alpha-D-glucopyranose (6) in CD3CN (97.2 v %) and D2O (2.8 v %) containing DCl (2.8 x 10(-4) M) was followed by H-1 NMR spectroscopy, an intermediate was detected that may be the corresponding hemi ortho ester. Evidence was also obtained for the incursion of a hemi ortho ester in the hydrolysis of 1,2-O-(alpha-exo,4-dimethoxy-benzylidene)-alpha-D-glucopyranose (14) under similar conditions. The proportions of the hydrolysis products of 6, 1-O-acetyl-alpha-D-glucopyranose (13), and 2-O-acetyl-alpha-D-glucopyranose (12) depend on acid concentration with more of the former being formed at the higher acid concentrations. When the hydrolysis of 14 was studied at higher acid concentrations (DCl, 0.17 M) the intermediate cation 15 was detected. Evidence was obtained by O-18-labeled studies for decomposition of this by attack of water at C-1 of the glucopyranose ring and by an attack at the pro-acyl carbon of the dioxolanylium ion depending on the reaction conditions. In the hydrolysis of the ortho esters derived from beta-D-mannopyranose, tricyclic 1,2,6-ortho esters were detected in solvents of low water content and when the concentration of DCl was 0.33 M, the intermediate cation was also detected. The kinetics of hydrolysis of the two series of ortho esters were studied by UV spectrophotometry, and evidence was obtained that the 1,2-O-(alpha-exo-alkoxy-4-methoxybenzylidene)-alpha-D-glucopyranoses reacted with rate-limiting breakdown of intermediate hemi ortho ester at high acid concentrations. Evidence for similar behavior was obtained for the hydrolysis of the analogous glucose orthobenzoate esters and mannose 4-methoxyorthobenzoate esters, but the other compounds studied showed no evidence for a change in the rate-determining step of their hydrolyses or else showed complex kinetics on hydrolysis indicative that formation and breakdown of the hemi ortho ester were proceeding at comparable rates.
• Preparation of a glycosyl donor suitable for synthesis of glycoprotein “core” oligosaccharides
  作者：Charng-Ming Liu、Christopher D. Warren、Roger W. Jeanloz

  DOI：10.1016/0008-6215(85)85203-4

  日期：1985.2

  2-O-Acetyl-3-O-allyl-4-O-benzyl-6-O-tert-butyldiphenylsilyl-D-gluc opyranosyl chloride (14), a glycosyl donor suitable for synthesis of oligosaccharides corresponding to the N-glycoprotein saccharide "core", was synthesized by an efficient, six-stage route from 3,4,6-tri-O-acetyl-1,2-O-[1-(exo-ethoxy)ethylidene)-alpha-D-glucopyranos e. Silver triflate-promoted coupling of 14 with benzyl 2-acetamido-3

  2-O-乙酰基-3-O-烯丙基-4-O-苄基-6-O-叔丁基二苯基甲硅烷基-D-葡萄糖吡喃糖基氯（14），一种适合合成对应于N-糖蛋白糖的寡糖的糖基供体“核心”是由3,4,6-三-O-乙酰基-1,2-O- [1-（外-乙氧基）亚乙基）-α-D-吡喃葡萄糖通过高效的六步路线合成的。由三氟甲磺酸银促进的14与苄基2-乙酰氨基-3,6-二-O-苄基-2-脱氧-α-D-吡喃葡萄糖苷的偶联产生了受保护的与β-D-（1 ---- 4）连接的二糖收率38％，但也发生了主要的副反应。当在偶联反应之前将叔丁基二苯基甲硅烷基从14定量除去后再取代时，糖苷化的产率增加到55％，并且避免了主要副产物。