3'-O-mesyl-5'-O-tosylthymidine | 140175-69-5

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 3'-O-mesyl-5'-O-tosylthymidine
• 英文别名: Mes(-3)[Tos(-5)]2-deoxy-D-eryPenf(b)-thymin-1-yl；[(2R,3S,5R)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)-3-methylsulfonyloxyoxolan-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 140175-69-5
• 化学式: C₁₈H₂₂N₂O₉S₂
• 分子量: 474.513
• InChiKey: WYYPUHQUHJEDGL-ARFHVFGLSA-N

物化性质

• 密度：
  1.54±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  162
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3'-O-mesyl-5'-O-tosylthymidine 在 lithium aluminium tetrahydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙腈 为溶剂， 反应 106.0h， 生成 3',5'-dithiothymidine
  参考文献：
  名称：

  二硫骨架核酸的研究：第 2 部分. 3',5'-二硫胸苷的高效合成

  摘要：

  描述了一种新的和方便的合成 3',5'-二硫胸苷的方法。在此过程中，DBU 用于形成 2,3'-脱水胸苷的分子内环，然后使用硫代乙酸作为溶剂和亲核试剂以生产 S-乙酰基-3'-硫代胸苷。应用非常有效的脱保护步骤来提供目标化合物，这可以避免硫醇基团的氧化。并且发现关键中间体 5'-O-tosyl-2,3'-脱水胸苷对不同的亲核试剂具有区域选择性。

  DOI：

  10.1246/cl.2005.432
• 作为产物：
  描述：

  1-(2-deoxy-3-O-methanesulfonyl-5-O-trityl-β-D-ribopentofuranosyl)thymine 在 吡啶 、 4-二甲氨基吡啶 、 三氟乙酸 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 12.08h， 生成 3'-O-mesyl-5'-O-tosylthymidine
  参考文献：
  名称：

  Nucleoside sultones: synthons for the preparation of novel nucleotide analogs. 1. Synthesis and ring-opening reactions

  摘要：

  Treatment of either the 5'-O-tosyl or the 5'-O-mesyl derivative of 3'-O-mesylthymidine with lithium acetylide-ethylenediamine complex in DMSO affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-l-(3,4-dihydro-5-methyl-2, 4-dioxo-1(2H)-pyrimidinyl)-beta-D-erythro-hexofuranuronosulfonic acid (2). Similarly, the 5'-O-tosyl or 5'-O-mesyl derivative of 1-(2-deoxy-3-O-mesyl-beta-D-threo-pentofuranosyl)thymine affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-1-(3,4-dihydro-5-methyl-2,4-dioxo-1(2H)-pyrimidinyl)-beta-D-threo-hexofuranurononsulfonic acid (5). Sultone 5 reacts with a variety of nucleophiles to afford good yields of the corresponding 3'-substituted sulfonate salts (6, 7, 9, and 10) and, in some cases, the unsaturated nucleoside 8. Sultone 2 was generally much less susceptible to ring opening by nucleophiles. However, in the presence of base, nucleophilic substitution with azide ion did proceed via the intermediate anhydronucleoside, 11, to afford 6. Reaction of 2 with EtOH-NaOH afforded a 1:1 mixture of the epimeric 3'-hydroxy compounds 9 and 12. The above sulfonate salts represent interesting new isosteres of nucleoside 5'-O-phosphates.

  DOI：

  10.1021/jo00036a014

文献信息

• Study on Disulfur-backboned Nucleic Acid: Part 2. Efficient Synthesis of 3′,5′-Dithiothymidine
  作者：Hua Wang、Changmei Cheng、Hongchao Zheng、Xiaohong Liu、Chang Fang、Shanshan Xu、Yufen Zhao

  DOI：10.1246/cl.2005.432

  日期：2005.3

  novel and convenient procedure for synthesizing 3',5'-dithiothymidine was described. In this procedure, DBU was used to form the intramolecular ring of 2,3'-anhydrothymidine and then the thioacetic acid was used as solvent as well as the nucleophilic reagent to produce S-acetyl-3'-thiothymidine. A very efficient deprotection step was applied to afford the target compound, which can avoid the oxidization

  描述了一种新的和方便的合成 3',5'-二硫胸苷的方法。在此过程中，DBU 用于形成 2,3'-脱水胸苷的分子内环，然后使用硫代乙酸作为溶剂和亲核试剂以生产 S-乙酰基-3'-硫代胸苷。应用非常有效的脱保护步骤来提供目标化合物，这可以避免硫醇基团的氧化。并且发现关键中间体 5'-O-tosyl-2,3'-脱水胸苷对不同的亲核试剂具有区域选择性。
• Nucleoside sultones: synthons for the preparation of novel nucleotide analogs. 1. Synthesis and ring-opening reactions
  作者：Peter A. Crooks、Robert C. Reynolds、Joseph A. Maddry、Anita Rathore、M. Shamim Akhtar、John A. Montgomery、John A. Secrist

  DOI：10.1021/jo00036a014

  日期：1992.5

  Treatment of either the 5'-O-tosyl or the 5'-O-mesyl derivative of 3'-O-mesylthymidine with lithium acetylide-ethylenediamine complex in DMSO affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-l-(3,4-dihydro-5-methyl-2, 4-dioxo-1(2H)-pyrimidinyl)-beta-D-erythro-hexofuranuronosulfonic acid (2). Similarly, the 5'-O-tosyl or 5'-O-mesyl derivative of 1-(2-deoxy-3-O-mesyl-beta-D-threo-pentofuranosyl)thymine affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-1-(3,4-dihydro-5-methyl-2,4-dioxo-1(2H)-pyrimidinyl)-beta-D-threo-hexofuranurononsulfonic acid (5). Sultone 5 reacts with a variety of nucleophiles to afford good yields of the corresponding 3'-substituted sulfonate salts (6, 7, 9, and 10) and, in some cases, the unsaturated nucleoside 8. Sultone 2 was generally much less susceptible to ring opening by nucleophiles. However, in the presence of base, nucleophilic substitution with azide ion did proceed via the intermediate anhydronucleoside, 11, to afford 6. Reaction of 2 with EtOH-NaOH afforded a 1:1 mixture of the epimeric 3'-hydroxy compounds 9 and 12. The above sulfonate salts represent interesting new isosteres of nucleoside 5'-O-phosphates.