methyl 6-O-tosyl-α-D-galactopyranoside | 34698-19-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-tosyl-α-D-galactopyranoside
• 英文别名: methyl 6-O-(4-toluenesulfonyl)-α-D-galactopyranoside；methyl 6-O-(p-tolylsulfonyl)-α-D-galactopyranoside；methyl 6-O-p-tolylsulfonyl-α-D-galactopyranoside；methyl 6-O-p-tolsulfonyl-α-D-galactopyranoside；methyl-6-O-tosyl-α-D-galactopyranoside；methyl-[O⁶-(toluene-4-sulfonyl)-α-D-galactopyranoside]；((2R,3R,4S,5R,6S)-3,4,5-Trihydroxy-6-methoxytetrahydro-2H-pyran-2-yl)methyl 4-methylbenzenesulfonate；[(2R,3R,4S,5R,6S)-3,4,5-trihydroxy-6-methoxyoxan-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 34698-19-6
• 化学式: C₁₄H₂₀O₈S
• 分子量: 348.374
• InChiKey: DBMMVDKCWRGJEG-HTOAHKCRSA-N

物化性质

• 熔点：
  170 °C
• 沸点：
  550.2±50.0 °C(Predicted)
• 密度：
  1.47±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  131
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 6-O-tosyl-α-D-galactopyranoside 在 sodium hydroxide 、 丙酮 、 silver(l) oxide 作用下， 生成 methyl 3,6-anhydro-2,4-di-O-methyl-α-D-galactopyranoside
  参考文献：
  名称：

  Haworth et al., Journal of the Chemical Society, 1940, p. 620,629

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2:3,4-二-o-异亚丙基-6-o-对甲苯磺酰基-alpha-D-半乳糖 在 盐酸 、 甲醇 、 溶剂黄146 作用下， 生成 methyl 6-O-tosyl-α-D-galactopyranoside
  参考文献：
  名称：

  Ohle; Thiel, Chemische Berichte, 1933, vol. 66, p. 525,531

  摘要：

  DOI：

文献信息

• Chiral Benzazaborole‐Catalyzed Regioselective Sulfonylation of Unprotected Carbohydrate Derivatives
  作者：Satoru Kuwano、Yusei Hosaka、Takayoshi Arai

  DOI：10.1002/chem.201903443

  日期：2019.10.8

  Chiral benzazaborole-catalyzed regioselective sulfonylations of unprotected carbohydrate derivatives have been developed. This methodology enables direct regioselective functionalization of the secondary OH group in carbohydrate in the presence of the primary OH group. By using the chiral organoboron catalysis, kinetic resolution of the carbohydrate derivatives was also achieved.

  已经开发了未保护的碳水化合物衍生物的手性苯并氮杂硼烷催化的区域选择性磺酰化。该方法使得在存在伯OH基的情况下，能够直接对碳水化合物中的仲OH基进行区域选择性官能化。通过使用手性有机硼催化，还实现了碳水化合物衍生物的动力学拆分。
• SYNTHESIS OF 6-AMINO-6-DEOXY-2,3,4,5- TETRA-O-METHYL-D-GALACTONIC ACID, A KEY PRECURSOR OF A STEREOREGULAR POLYAMIDE1
  作者：Carmen Zaliz、Oscar Varela

  DOI：10.1081/car-100108283

  日期：——

  α-pyranoside (6). Methylation of the free hydroxyl groups of 5 and 6 gave the respective per-O-methyl derivatives 7 and 8. In order to maintain the size of the sugar ring during the sequence, compound 8 was alternatively prepared from 9, by acetylation, substitution by azide and per-O-methylation. Hydrolysis of the glycoside followed by oxidation and further 5-O-methylation afforded the 6-azido-6-deoxy carboxylic

  标题化合物（17）是通过两个替代序列合成的，从D-半乳糖二丙酮化物（1）和甲基6 - O-甲苯磺酰基-α- D-吡喃半乳糖苷（9）开始。化合物1被转化为6-溴-6-脱氧衍生物2或被甲磺化为3。用叠氮化钠对2和3中的离去基团进行亲核取代，生成6-叠氮基6-脱氧衍生物4，在酸性条件下用甲醇处理后，得到相应的甲基β-呋喃糖苷（5）和α-吡喃糖苷（6）。的游离羟基基团的甲基化5和6，得到相应的per- ø -甲基衍生物7和8。为了在序列中维持糖环的大小，可替代地由9通过乙酰化，叠氮化物取代和过-O-甲基化制备化合物8。糖苷水解，然后氧化并进一步5- O-甲基化，得到6-叠氮基-6-脱氧羧酸16，其通过叠氮化物官能团的氢解转化为17（从9得到的总产率为38％）。
• Thiosugar nucleotide analogs: Synthesis of 5′-(2,3,4-tri-O-acetyl-6-S-acetyl-6-thio-α-d-galactopyranosyl diphosphate)
  作者：Jordan Elhalabi、Kevin G. Rice

  DOI：10.1016/s0008-6215(02)00210-0

  日期：2002.11

  The synthesis of a novel analog of uridine diphosphate galactose (UDP-Gal) is described. A sulfur atom was inserted into the 6-position of galactose to give uridine 5'-(2,3,4-tri-O-acetyl-6-S-acetyl-6-thio-alpha-D-galactopyranosyl diphosphate). This peracetylated thiol analogue of UDP-Gal has been synthesized in nine steps starting from methyl alpha-D-galactopyranoside in an overall yield of 3%.

  描述了尿苷二磷酸半乳糖（UDP-Gal）的新型类似物的合成。将硫原子插入半乳糖的6-位，得到尿苷5'-（2,3,4-三-O-乙酰基-6-S-乙酰基-6-硫代-α-D-吡喃半乳糖基二磷酸酯）。UDP-Gal的这种全乙酰化硫醇类似物已从甲基α-D-吡喃半乳糖苷开始以9个步骤合成，总收率为3％。
• Analogues of Moranoline and Mdl 73945. Methyl 6(5)-Deoxy-6(5)-(Morpholin-4-Yl)-α-D-Glycosides as Glucosidase Inhibitors
  作者：El Sayed H. El Ashry、Adel A.-H. Abdel-Rahman、Mohamed Kattab、Aida H. Shobier、Richard R. Schmidt

  DOI：10.1080/07328300008544083

  日期：2000.1

  Methyl 2,3,4-tri-O-acetyl-6-O-(p-tolylsulfonyl)-α-D-glucopyranoside (6), or its iodo analogue 7, were subjected to nucleophilic displacement with morpholine to give 8, deacetylation of which gave methyl 6-deoxy-6-(morpholin-4-yl)-α-D-glucopyranoside (3). Similarly, 11, 12 and 21 were prepared. The 6-deoxy-6-iodo derivative 16 was subjected to nucleophilic displacement with morpholine and subsequent

  摘要将甲基2,3,4-三-O-乙酰基-6-O-（对甲苯磺酰基）-α-D-吡喃葡萄糖苷（6）或其碘代类似物7进行吗啉的亲核置换，得到8，脱乙酰基得到甲基6-脱氧-6-（吗啉-4-基）-α-D-吡喃葡萄糖苷（3）。类似地，准备了11、12和21。用吗啉对6-脱氧-6-碘衍生物16进行亲核置换，然后乙酰化，得到15。15的脱乙酰基得到17。对甜杏仁中β-D-葡糖苷酶的抑制作用以及使用邻硝基苯的动力学研究以β-D-吡喃葡萄糖苷为底物的K i值与1-脱氧野n霉素的顺序相同，而对于3，观察到的K i值较小。
• S-Acetyl migration in synthesis of sulfur-containing glycosides
  作者：Yixuan Zhou、Xiaoling Zhang、Bo Ren、Bin Wu、Zhichao Pei、Hai Dong

  DOI：10.1016/j.tet.2014.07.014

  日期：2014.9

  Unexpected products are often found in the synthesis of sulfur-containing glycosides where the sulfur-containing group is acquired through substitution of a leaving group by a thioacetate reagent. Thus low yields have to be born. The reason has been disclosed to originate from the basicity and nucleophilicity of sulfur atom leading to a thioacetyl group migration in this study. The migration may occur

  在含硫糖苷的合成中经常发现意外的产物，其中含硫基团是通过用硫代乙酸盐试剂取代离去基团而获得的。因此必须产生低产量。在本研究中，已公开原因是由于硫原子的碱性和亲核性导致硫代乙酰基迁移。可能通过五元或六元环四面体中间体发生迁移，然后裂解该中间体的CS键以形成巯基阴离子，然后另一个乙酰基从硫代乙酸盐试剂迁移至巯基阴离子，从而导致意外的产物乙酰化的邻近羟基。迁移的发生可能取决于硫代乙酸盐试剂的浓度以及底物本身的空间和立体电子效应。基于这些结果，可以大大提高合成含硫糖苷的产率。