O-[5'-O-(4,4'-dimethoxytrityl)thymidin-3'-yl] S-(2,4-dichlorobenzyl) O-(3'-O-acetylthymidin-5'-yl) phosphorodithioate | 118149-27-2

• 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: O-[5'-O-(4,4'-dimethoxytrityl)thymidin-3'-yl] S-(2,4-dichlorobenzyl) O-(3'-O-acetylthymidin-5'-yl) phosphorodithioate
• 英文别名: [(2R,3S,5R)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-[(2,4-dichlorophenyl)methylsulfanyl]phosphinothioyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate
• CAS: 118149-27-2
• 化学式: C₅₀H₅₁Cl₂N₄O₁₃PS₂
• 分子量: 1081.99
• InChiKey: PNMYZVGEVHHXJW-UZUCDNOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  72
• 可旋转键数：
  20
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  247
• 氢给体数：
  2
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  O-[5'-O-(4,4'-dimethoxytrityl)thymidin-3'-yl] S-(2,4-dichlorobenzyl) O-(3'-O-acetylthymidin-5'-yl) phosphorodithioate 在 苯硫酚 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 生成 O-5'-O-(Di-p-methoxytrityl)thymidin-3'-yl, O-3'-O-(acetyl)thymidin-5'-yl-phosphorodithioate
  参考文献：
  名称：

  Brill, Wolfgang K.-D.; Nielsen, John; Caruthers, Marvin H., Journal of the American Chemical Society, 1991, vol. 113, # 10, p. 3972 - 3980

  摘要：

  DOI：
• 作为产物：
  描述：

  5’-(4,4’-二甲氧基三苯基)-3’-脱氧胸苷 2’-(2-氰乙基-N,N-二异丙基)亚磷酰胺 在 N-甲基咪唑 、 2,6-二甲基吡啶 、 四氮唑 、 triisopropylbenzenesulfonylchloride 、 sulfur 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.17h， 生成 O-[5'-O-(4,4'-dimethoxytrityl)thymidin-3'-yl] S-(2,4-dichlorobenzyl) O-(3'-O-acetylthymidin-5'-yl) phosphorodithioate
  参考文献：
  名称：

  通过磷酸三酯方法合成二核苷和二核苷酸二硫代磷酸酯

  摘要：

  5'-O-二甲氧基三苯甲基和S-保护的胸苷-3'-硫代磷酸二硫酯，3'-O-乙酰基胸苷或胸苷-3'-O- [β-氰基乙基-（S-2,4-二氯苄基）]-二硫代磷酸酯，1 -甲基咪唑与2,4,6-三异丙基苯磺酰氯反应生成二核苷二硫代磷酸酯的产率很高。

  DOI：

  10.1016/s0040-4039(00)88887-5

文献信息

• Synthesis of oligonucleotide phosphorodithioates
  作者：G. Beaton、W.K.-D. Brill、A. Grandas、Y.-X. Ma、J. Nielsen、E. Yau、M.H. Caruthers

  DOI：10.1016/s0040-4020(01)81775-0

  日期：1991.1

  The synthesis of DNA containing sulfur at the two nonbonding internucleotide valencies is reported. Several different routes using either tervalent or pentavalent mononucleotide synthons are described.

  据报道，在两个非键合核苷酸间价态上合成了含硫的DNA。描述了使用三价或五价单核苷酸合成子的几种不同途径。
• Synthesis and characterization of dinucleoside phosphorodithioates
  作者：John Nielsen、Wolfgang K.-D Brill、Marvin H Caruthers

  DOI：10.1016/0040-4039(88)85045-7

  日期：1988.1

  Dinucleoside phosphoramidites, H2S, and tetrazole react to form dinucleoside H-phosphonothioates. Oxidation with sulfur yields phosphorodithioates. Iodine oxidation in the presence of amines, alcohols, or water yields phosphorothioamidates, thiotriesters or thiodiesters.

  二核苷亚磷酰胺，H 2 S和四唑反应形成二核苷H-硫代磷酸酯。用硫氧化产生二硫代磷酸酯。在胺，醇或水的存在下碘氧化可生成硫代磷酸氨基甲酸酯，硫代三酸酯或硫代二酯。
• Solid phase synthesis of oligodeoxynucleoside phosphorodithioates by a phosphotriester method using a chemoselective coupling reagent
  作者：Jan Kehler、Ask Püschl、Otto Dahl

  DOI：10.1016/0040-4039(96)01820-5

  日期：1996.10

  A phosphotriester method has been developed for solid phase synthesis of oligodeoxynucleoside phosphorodithioates. Couplings are performed by chemoselective oxygen activation of protected nucleoside dithiophosphate anions 1, 7, 8, 9 with 4-nitro-6-trifluoromethylbenzotriazol-1-yl-oxy-tris(pyrrolidine)-phosphonium hexafluorophosphate (PyFNOP). Under optimised conditions coupling yields are above 95%

  已经开发了磷酸三酯方法用于固相合成寡脱氧核苷二硫代磷酸酯。偶联通过化学选择性氧激活保护的核苷二硫代磷酸盐阴离子进行1，7，8，9与4-硝基-6- trifluoromethylbenzotriazol -1-基-氧基-三（吡咯烷）鏻六氟磷酸盐（PyFNOP）。在最佳条件下，偶联10-20分钟的收率可达95％以上，解封后的产品不含硫代磷酸酯污染（检出限为0.5％）。
• Solution Phase Synthesis of Dithymidine Phosphorodithioate Using New S-Protecting Groups in Combination with a Chemoselective Coupling Reagent (PyNOP)
  作者：Jan Kehler、Ask Püschl、Otto Dahl

  DOI：10.1080/07328319708002518

  日期：1997.1

  A method for the synthesis of O-thymidin-3'-yl S-alkyl dithiophosphate monomers 1 with different S-protecting groups has been developed. These for solution phase synthesis of dithymidine phosphorodithioate by a new method. Coupling reactions are fast (15 min.) and the products phosphorothioate contaminations.
• Synthesis of Oligodeoxynucleoside Phosphoro-Monothioates and Phosphorodithioates by a Phosphotriester Method
  作者：Jan Kehler、Ask Püschl、Otto Dahl

  DOI：10.1080/07328319708006243

  日期：1997.7

  A phosphotriester method for the synthesis of dithymidine phosphoromonothioates and phosphorodithioates with new S-protecting groups has been investigated. Four of the S-protecting groups possesed catalytic activity, however side reactions occurred during deprotection. The best S-protecting group was 4-chloro-2-nitrobenzyl which could be removed with a minimum of side reactions (0.3 %). The coupling reagent PyFNOP (14) gave protected dithymidine phosphoromonothioate in 96 % yield after 15 min coupling. Furthermore PyFNOP chemoselectively activates oxygen in nucleoside phosphorodithioate monomers 9 and can be used for the synthesis of oligodeoxynucleoside phosphorodithioates with mixed base sequences.