5'-O-DMT-thymidine 3'-O-(2-thio-1,3,2-oxathiaphospholane) | 179090-12-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 5'-O-DMT-thymidine 3'-O-(2-thio-1,3,2-oxathiaphospholane)
• 英文别名: 1-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[(2-sulfanylidene-1,3,2lambda5-oxathiaphospholan-2-yl)oxy]oxolan-2-yl]-5-methylpyrimidine-2,4-dione；1-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[(2-sulfanylidene-1,3,2λ5-oxathiaphospholan-2-yl)oxy]oxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 179090-12-1
• 化学式: C₃₃H₃₅N₂O₈PS₂
• 分子量: 682.755
• InChiKey: WRFHHABBLFBECG-FHAUPYODSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  46
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  162
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  5'-O-DMT-thymidine 3'-O-(2-thio-1,3,2-oxathiaphospholane) 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 triethylamine tris(hydrogen fluoride) 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以78%的产率得到O-[5'-O-(4,4'-dimethoxytrityl)thymidin-3'-yl] hydrogen thiophosphorofluoridate
  参考文献：
  名称：

  Synthesis and chemical and enzymatic reactivity of thymidine 3′-O- and 5′-O-phosphorofluoridothioates

  摘要：

  5′-O-或3′-O-保护的胸苷3′-O-或5′-O-(2-硫代-1,3,2-氧硫磷烷)与三乙基氨氟化物在DBU存在下反应，随后脱保护得到胸苷3′-O-和5′-O-磷氟硫酸酯；后者通过蛇毒磷酸二酯酶进行立体选择性水解。

  DOI：

  10.1039/a706636h
• 作为产物：
  描述：

  在 sulfur 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 5'-O-DMT-thymidine 3'-O-(2-thio-1,3,2-oxathiaphospholane)
  参考文献：
  名称：

  Diastereomers of Nucleoside 3'-O-(2-Thio-1,3,2-oxathia(selena)phospholanes): Building Blocks for Stereocontrolled Synthesis of Oligo(nucleoside phosphorothioate)s

  摘要：

  Diastereomerically pure 5'-O-DMT-nucleoside 3'-O-(2-thio-1,3,2-oxathiaphospholanes) (3) and their oxathiaphospholane ring-substituted analogues (20) were used for the synthesis of stereoregular oligo(nucleoside phosphorothioate)s (S-Oligos). The oxathiaphospholane ring-opening condensation requires the presence of strong organic base, preferably DBU. The yield of a single coupling step is ca. 95% and resulting S-Oligos are free of nucleobase- and sugar-phosphorothioate backbone modifications. The diastereomeric purity of products was estimated on the basis of diastereoselective degradation with Nuclease P1 and a mixture of snake venom phosphodiesterase and Serratia marcescens endonuclease. Thermal dissociation studies of heteroduplexes S-Oligos/DNA and S-Oligos/RNA showed that their stability is stereochemistry- and sequence-dependent.

  DOI：

  10.1021/ja00154a001

文献信息

• Thiophosphorylation of Biologically Relevant Alcohols by the Oxathiaphospholane Approach
  作者：Magdalena Olesiak、Danuta Krajewska、Ewa Wasilewska、Dariusz Korczyński、Janina Baraniak、Andrzej Okruszek、Wojciech J. Stec

  DOI：10.1055/s-2002-31913

  日期：——

  2-Alkoxy-2-thiono-1,3,2-oxathiaphospholanes are readily transformed into phosphorothioate monoesters of the corresponding alcohols in a one-pot process, involving the reaction with 3-hydroxypropionitrile in the presence of DBU, followed by treatment with aqueous ammonia. In this way a series of nucleoside-3′-O- and 5′-O-phosphorothioates were prepared, as well as phosphorothioate derivatives of selected polyols.

  2-烷氧基-2-硫代-1,3,2-氧硫磷烷可以方便地通过一步法转化为相应醇的磷酸硫代单酯，该方法涉及在DBU存在下与3-羟基丙腈反应，随后用氨水处理。通过这种方法制备了一系列核苷-3′-O-和5′-O-磷酸硫代酯，以及选定多元醇的磷酸硫代衍生物。
• DBU-assisted 1,3,2-oxathiaphospholane ring-opening condensation with selected O-, S-, N- and C-nucleophiles
  作者：Konrad Misiura、Daria Szymanowicz、Magdalena Olesiak、Wojciech J. Stec

  DOI：10.1016/j.tetlet.2004.04.012

  日期：2004.5

  The reactivity of protected thymidine 3'-O- and 5'-O-(2-thio-1,3,2-oxathiaphospholanes) towards various nucleophiles in the presence of DBU is presented and mechanistic implications are discussed. (C) 2004 Elsevier Ltd. All rights reserved.