ethyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-α-L-rhamnopyranoside | 172361-34-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-α-L-rhamnopyranoside
• 英文别名: [(3aR,4S,6S,7S,7aR)-4-ethylsulfanyl-2,2,6-trimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl] acetate
• CAS: 172361-34-1
• 化学式: C₁₃H₂₂O₅S
• 分子量: 290.381
• InChiKey: IQAXLPWFGATXIB-CFVLRQLYSA-N

物化性质

• 沸点：
  367.2±42.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  79.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-α-L-rhamnopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 4 A molecular sieve 、 碘 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 12.17h， 生成 Bz(-2)[Bz(-3)]Rha4Ac(a1-3)[Bz(-2)][Bz(-4)][Bz(-6)]Gal(b)-O-EtTMS
  参考文献：
  名称：

  Synthesis of a Pentasaccharide Epitope for the Investigation of Carbohydrate-Protein Interactions

  摘要：

  Pyranose residues of a polysaccharide that are not involved in the principal sugar-protein antibody combining site, filled by trisaccharide 1, cause a 50-fold reduction in intrinsic affinity. The antibody is crystallographically characterized, and the residue responsible for the lost binding energy has been identified as the terminal disaccharide Rha-->Gal of pentasaccharide 5. This disaccharide segment of 5 may avoid protein contact by adopting the ''anti'' conformer about the preceding Man-Rha glycosidic linkage. Monosaccharide thioglycoside synthons 6-9 were used in NIS-promoted glycosylations to synthesize the pentasaccharide as a glycoside that was suitable for binding and solution conformational studies. Disaccharide 29 was obtained upon the addition of rhamnose building unit 6 to the (trimethylsilyl)ethyl galactopyranoside 10 followed by protecting group manipulation. The sequential addition of 7-9 to 29 afforded the pentasaccharide derivative 35 bearing a 2-O-benzoate group suited for subsequent 1,2-trans-glycoside synthesis following its conversion to a glycosyl imidate. In order to preserve the integrity of the 3,6-dideoxyhexopyranosyl glycosidic bond during cleavage of the (trimethylsilyl)ethyl group leading to the imidate 39, it was essential to convert the benzylated pentasaccharide target 35 into its fully acylated derivative 37. Pentasaccharide 5 was obtained by transesterification of the protected glycoside 40 formed via 39. Qualitative NOE measurements suggest a predominant solution conformation for 5 that cannot be adopted in the bound state due to protein-oligosaccharide clashes at the periphery of the binding site.

  DOI：

  10.1021/jo00127a043
• 作为产物：
  描述：

  2,2-二甲氧基丙烷 在 吡啶 、 对甲苯磺酸 作用下， 反应 4.5h， 生成 ethyl 4-O-acetyl-2,3-O-isopropylidene-1-thio-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of a Pentasaccharide Epitope for the Investigation of Carbohydrate-Protein Interactions

  摘要：

  Pyranose residues of a polysaccharide that are not involved in the principal sugar-protein antibody combining site, filled by trisaccharide 1, cause a 50-fold reduction in intrinsic affinity. The antibody is crystallographically characterized, and the residue responsible for the lost binding energy has been identified as the terminal disaccharide Rha-->Gal of pentasaccharide 5. This disaccharide segment of 5 may avoid protein contact by adopting the ''anti'' conformer about the preceding Man-Rha glycosidic linkage. Monosaccharide thioglycoside synthons 6-9 were used in NIS-promoted glycosylations to synthesize the pentasaccharide as a glycoside that was suitable for binding and solution conformational studies. Disaccharide 29 was obtained upon the addition of rhamnose building unit 6 to the (trimethylsilyl)ethyl galactopyranoside 10 followed by protecting group manipulation. The sequential addition of 7-9 to 29 afforded the pentasaccharide derivative 35 bearing a 2-O-benzoate group suited for subsequent 1,2-trans-glycoside synthesis following its conversion to a glycosyl imidate. In order to preserve the integrity of the 3,6-dideoxyhexopyranosyl glycosidic bond during cleavage of the (trimethylsilyl)ethyl group leading to the imidate 39, it was essential to convert the benzylated pentasaccharide target 35 into its fully acylated derivative 37. Pentasaccharide 5 was obtained by transesterification of the protected glycoside 40 formed via 39. Qualitative NOE measurements suggest a predominant solution conformation for 5 that cannot be adopted in the bound state due to protein-oligosaccharide clashes at the periphery of the binding site.

  DOI：

  10.1021/jo00127a043

文献信息

• Mild and Efficient Hydrolysis of Thioglycosides to Glycosyl Hemiacetals Using <i>N</i>-Iodosaccharin
  作者：Anup Misra、Pintu Mandal

  DOI：10.1055/s-2007-977412

  日期：——

  A convenient methodology has been developed for the mild hydrolysis of thioglycosides to the corresponding hemiacetals using N-iodosaccharin without any requirement of co-activator. Most of the functional groups used for the protecting group ­manipulation of carbohydrates remain unaffected under the reaction conditions.

  已开发出一种便捷的方法，利用N-碘代糖精在无需任何共活化剂的条件下对硫苷进行温和水解，生成相应的半缩醛。在反应条件下，大多数用于糖类保护基操作的功能团保持不受影响。
• Synthetic and immunological studies of <i>Salmonella</i> Enteritidis O-antigen tetrasaccharides as potential anti-<i>Salmonella</i> vaccines
  作者：Chang-Xin Huo、Debashis Dhara、Scott M. Baliban、Setare Tahmasebi Nick、Zibin Tan、Raphael Simon、Anup Kumar Misra、Xuefei Huang

  DOI：10.1039/c8cc08622b

  日期：——

  The conjugate of a synthetic Salmonella Enteritidis tetrasaccharide with bacteriophage Qβ induced powerful anti-glycan IgG responses for complete protection from lethal challenges of bacteria.

  合成的沙门氏菌Enteritidis四糖与噬菌体Qβ的结合诱导了强大的抗糖基IgG反应，从而完全保护免受细菌致命挑战。
• Syntheses of <i>Salmonella</i> Paratyphi A Associated Oligosaccharide Antigens and Development towards Anti‐Paratyphoid Fever Vaccines
  作者：Debashis Dhara、Scott M. Baliban、Chang‐Xin Huo、Zahra Rashidijahanabad、Khandra T. Sears、Setare Tahmasebi Nick、Anup Kumar Misra、Sharon M. Tennant、Xuefei Huang

  DOI：10.1002/chem.202002401

  日期：2020.12.4

  With the emergence of multidrug resistant Salmonella strains, the development of anti‐Salmonella vaccines is an important task. Currently there are no approved vaccines against Salmonella Paratyphi A, the leading cause of paratyphoid fever. To fill this gap, oligosaccharides corresponding to the O‐polysaccharide repeating units from the surface of Salmonella Paratyphi A have been synthesized through

  随着多重耐药沙门氏菌菌株的出现，抗沙门氏菌疫苗的开发成为一项重要任务。目前还没有批准针对甲型副伤寒沙门氏菌（副伤寒的主要原因）的疫苗。为了填补这一空白，通过聚合立体选择性糖基化合成了与甲型副伤寒沙门氏菌表面的O-多糖重复单元相对应的寡糖。合成聚糖抗原与强大的免疫原性载体系统——噬菌体 Qβ 结合。由此产生的构建体能够引发强烈且持久的抗聚糖 IgG 抗体反应，该抗体反应对甲型副伤寒沙门氏菌相关聚糖具有高度选择性。明确的聚糖抗原的可用性使得能够确定多糖的一个重复单元足以诱导保护性抗体，并且主链上的帕拉糖残基和/或O-乙酰基修饰对于Qβ引发的抗体的识别非常重要‐四糖缀合物。免疫血清为小鼠提供了极好的保护，使其免受甲型副伤寒沙门氏菌的致命攻击，凸显了合成聚糖疫苗的潜力。
• β-<scp>l</scp>-Rhamnosylation and β-<scp>d</scp>-Mannosylation Mediated by 4-<i>O</i>-Ester Groups in a Weakly Nucleophilic Environment
  作者：Yongliang Zhang、Changsheng Chen、Yongtao Gao、Min Yang、Zehuan He、Bangzhi Zhang、Guofeng Gu、Bencan Tang、Feng Cai

  DOI：10.1021/acs.orglett.3c02566

  日期：2023.10.6

  eq-4-O-Acyl group directed β-rhamnosylation and β-mannosylation are achieved in a carborane or BARF anion formed weakly nucleophilic environment with the assistance of a 2,3-orthocarbonate group. The 4-O-acyl group plays a critical role in directing the β-selectivity, and the weakly coordinating anion is essential to amplify this direction. The orthocarbonate group could be readily removed with 1,3-propanediol

  eq -4- O -酰基定向的β-鼠李糖基化和β-甘露糖基化是在碳硼烷或BARF阴离子形成的弱亲核环境中在2,3-原碳酸酯基团的帮助下实现的。4- O-酰基在引导β-选择性方面起着关键作用，而弱配位阴离子对于放大该方向至关重要。在 BF 3 ·Et 2 O存在下，原碳酸酯基团可以很容易地用 1,3-丙二醇去除。
• Synthesis of the pentasaccharide repeating unit of latosillan
  作者：Yuxia Hua、Junjun Xiao、Yingshen Huang、Yuguo Du

  DOI：10.1016/j.carres.2005.11.007

  日期：2006.2

  A pentasaccharide, beta-D-Man-(1 -> 2)-[beta-D-GlcNAc-(1 -> 4)]-alpha-L-Rha-(1 -> 4)-alpha-L-Rha-(1 -> 4)-alpha-L-Rha-1-OC8H17, representing the repeating unit of latosillan, was convergently synthesized from the building blocks, ethyl 2,3-O-isopropylidene-1-thio-alpha-L-rhamnopyranoside, 2-O-acetyl-3,4,6-tri-O-belizyl-beta-D-glucopyranosyl trichloroacetimidate, and 3,4,6-tri-O-acetyl-2-deoxy-2phthalimido-beta-D-glueopyranosyl trichloroacetimidate under standard glycosylation conditions. The target pentasaccharide showed acceptable differentiation-inducing activity on HL-60 cell lines at the dosages of 10-50 mu g/mL. (c) 2005 Elsevier Ltd. All rights reserved.