3-deoxy-3-fluoro-6-O-benzoyl-1,2-O-isopropylidene-5-O-methanesulfonyl-α-D-glucofuranose | 1030022-54-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-deoxy-3-fluoro-6-O-benzoyl-1,2-O-isopropylidene-5-O-methanesulfonyl-α-D-glucofuranose
• 英文别名: [(2R)-2-[(3aR,5R,6S,6aS)-6-fluoro-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-methylsulfonyloxyethyl] benzoate
• CAS: 1030022-54-8
• 化学式: C₁₇H₂₁FO₈S
• 分子量: 404.413
• InChiKey: UXPJIYTVRYLMOG-JTTNIQEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-deoxy-3-fluoro-6-O-benzoyl-1,2-O-isopropylidene-5-O-methanesulfonyl-α-D-glucofuranose 在 sodium methylate 、 potassium acetate 、 硫脲 作用下， 以 甲醇 、 溶剂黄146 为溶剂， 生成 3-deoxy-5,6-di-O,S-acetyl-3-fluoro-1,2-O-isopropylidene-5-thio-α-D-gluco-pentofuranose
  参考文献：
  名称：

  Synthetic Studies on 2′-Substituted-4′-thiocytidine Derivatives as Antineoplastic Agents

  摘要：

  As potential antineoplastic agents, we have synthesized 4'-thioFAC and 4'-thiocytarazid by developing an alternative synthetic method. 4'-ThioFAC showed potent antineoplastic activities in vivo as well as in vitro.

  DOI：

  10.1080/15257779908041569
• 作为产物：
  描述：

  3-deoxy-1,2;5,6-di-O-isopropylidene-3-fluoro-α-D-glucofuranose 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.5h， 生成 3-deoxy-3-fluoro-6-O-benzoyl-1,2-O-isopropylidene-5-O-methanesulfonyl-α-D-glucofuranose
  参考文献：
  名称：

  An Alternative Synthesis of the Antineoplastic Nucleoside 4‘-ThioFAC and Its Application to the Synthesis of 4‘-ThioFAG and 4‘-Thiocytarazid

  摘要：

  Previously, we synthesized 4'-thioFAC, a novel antineoplastic cytosine nucleoside, by developing an original method. However, several problems remained. To overcome these problems, we have developed an alternative method far the synthesis of 4'-thionucleosides. In the original synthesis, carbons from C1 to C5 of D-glucose were used. The new method also starts from D-glucose but uses carbons closer to the tail (C2-C6). A dibenzoyl derivative obtained by this approach was brominated at the anomeric position to give a 1-bromide derivative. Fusion of the I-bromide and persilylated acetylcytosine, followed by deprotection, predominantly gave a beta-anomer of 4'-thioFAC. The reaction of 2,6-diaminopurine with the I-bromide in the presence of TMS triflate gave a glycosylated product in good yield. After deprotection, the resulting 1:1 anomeric mixture of free nucleosides was treated with adenosine deaminase to give a beta-anomer of 4'-thioFAG, a guanine congener of 4'-thioFAC, selectively. Using a similar approach, we synthesized 4'-thiocytarazid, which was not possible using the original method.

  DOI：

  10.1021/jo990958g

文献信息

• A concise synthesis of 3-fluoro-5-thio-xylo- and glucopyranoses, useful precursors towards their corresponding pyranonucleoside derivatives
  作者：Evangelia Tsoukala、Stella Manta、Niki Tzioumaki、George Agelis、Dimitri Komiotis

  DOI：10.1016/j.carres.2008.02.004

  日期：2008.5

  acetylated 3-fluoro-5-thio-D-xylopyranose with silylated thymine afforded the corresponding nucleoside. Selective benzoylation and direct methanesulfonylation of 3-fluoro-1,2-O-isopropylidene-alpha-D-glucofuranose gave the 6-O-benzoyl-5-O-methylsulfonyl derivative, which on treatment with sodium methoxide afforded the 5,6-anhydro derivative. Treatment of the latter with thiourea, followed by acetolysis

  1,2,4-三-O-乙酰基-3-脱氧-3-氟-5-硫代-D-吡喃葡萄糖，1,2,4,6-四-O-乙酰基-3-脱氧-的化学合成描述了3-氟-5-硫代-α-D-吡喃葡萄糖及其胸腺嘧啶的相应核苷。通过水解3-氟-1,2-O-异亚丙基-5-S-乙酰基5-硫代-的异亚丙基进行处理的3-氟-5-S-乙酰基-5-硫代-D-木呋喃糖的处理具有甲醇氨和直接乙酰化的D-木呋喃糖导致三乙酰化的3-脱氧-3-氟-5-硫代-D-木吡喃糖。乙酰化的3-氟-5-硫代-D-吡喃吡喃糖与甲硅烷基化的胸腺嘧啶缩合得到相应的核苷。3-氟-1,2-O-异亚丙基-α-D-葡萄糖呋喃糖的选择性苯甲酰化和直接甲磺酰化得到6-O-苯甲酰基-5-O-甲基磺酰基衍生物，其经甲醇钠处理后得到5,6-无水衍生物。后者用硫脲处理，然后进行乙酰分解，得到3-氟-5-S-乙酰基-6-O-乙酰基-1,2-O-异亚丙基-5-硫代-α-D-葡糖呋喃糖。将5
• An alternative synthesis of antineoplastic 4′-thiocytidine analogue 4′-thioFAC
  作者：Yuichi Yoshimura、Mikari Endo、Shinji Sakata

  DOI：10.1016/s0040-4039(99)00048-9

  日期：1999.3

  We have developed an alternative method for the synthesis of 2'-modified 4'-thionucleosides. The fusion of 3,5-di-O-benzoyl-1-bromo-2-deoxy-2-fluoro-4-thio-alpha-D-arabinofuranose, prepared from 1,2:5,6-diisopropylidene-alpha-D-allofuranose, with persilylated N-4-acetylcytosine predominantly gave a beta-anomer of protected 4'-thionucleoside, which was then deprotected to give 4'-thioFAC. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthetic Studies on 2′-Substituted-4′-thiocytidine Derivatives as Antineoplastic Agents
  作者：Yuichi Yoshimura、Mikari Endo、Kenji Kitano、Kohei Yamada、Shinji Sakata、Shinji Miura、Haruhiko Machida

  DOI：10.1080/15257779908041569

  日期：1999.4

  As potential antineoplastic agents, we have synthesized 4'-thioFAC and 4'-thiocytarazid by developing an alternative synthetic method. 4'-ThioFAC showed potent antineoplastic activities in vivo as well as in vitro.
• An Alternative Synthesis of the Antineoplastic Nucleoside 4‘-ThioFAC and Its Application to the Synthesis of 4‘-ThioFAG and 4‘-Thiocytarazid
  作者：Yuichi Yoshimura、Mikari Endo、Shinji Miura、Shinji Sakata

  DOI：10.1021/jo990958g

  日期：1999.10.1

  Previously, we synthesized 4'-thioFAC, a novel antineoplastic cytosine nucleoside, by developing an original method. However, several problems remained. To overcome these problems, we have developed an alternative method far the synthesis of 4'-thionucleosides. In the original synthesis, carbons from C1 to C5 of D-glucose were used. The new method also starts from D-glucose but uses carbons closer to the tail (C2-C6). A dibenzoyl derivative obtained by this approach was brominated at the anomeric position to give a 1-bromide derivative. Fusion of the I-bromide and persilylated acetylcytosine, followed by deprotection, predominantly gave a beta-anomer of 4'-thioFAC. The reaction of 2,6-diaminopurine with the I-bromide in the presence of TMS triflate gave a glycosylated product in good yield. After deprotection, the resulting 1:1 anomeric mixture of free nucleosides was treated with adenosine deaminase to give a beta-anomer of 4'-thioFAG, a guanine congener of 4'-thioFAC, selectively. Using a similar approach, we synthesized 4'-thiocytarazid, which was not possible using the original method.