[(2R,3R,4R,5R)-2-[[[(2R,3R,4R,5R)-5-(3-benzoyl-2,4-dioxopyrimidin-1-yl)-4-bis[(1-cyano-2-methylpropan-2-yl)oxy]phosphinothioyloxy-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]oxolan-3-yl]oxy-(2-cyanoethoxy)phosphoryl]oxymethyl]-4-benzoyloxy-5-[6-(dibenzoylamino)purin-9-yl]oxolan-3-yl] benzoate | 189145-17-3

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷酸
• 英文名称: [(2R,3R,4R,5R)-2-[[[(2R,3R,4R,5R)-5-(3-benzoyl-2,4-dioxopyrimidin-1-yl)-4-bis[(1-cyano-2-methylpropan-2-yl)oxy]phosphinothioyloxy-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]oxolan-3-yl]oxy-(2-cyanoethoxy)phosphoryl]oxymethyl]-4-benzoyloxy-5-[6-(dibenzoylamino)purin-9-yl]oxolan-3-yl] benzoate
• CAS: 189145-17-3
• 化学式: C₈₈H₈₀N₁₀O₂₁P₂S
• 分子量: 1707.67
• InChiKey: MMCXSXPINLUKRS-HMCYGQFDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.5
• 重原子数：
  122
• 可旋转键数：
  36
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  413
• 氢给体数：
  0
• 氢受体数：
  28

反应信息

• 作为反应物：
  描述：

  [(2R,3R,4R,5R)-2-[[[(2R,3R,4R,5R)-5-(3-benzoyl-2,4-dioxopyrimidin-1-yl)-4-bis[(1-cyano-2-methylpropan-2-yl)oxy]phosphinothioyloxy-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]oxolan-3-yl]oxy-(2-cyanoethoxy)phosphoryl]oxymethyl]-4-benzoyloxy-5-[6-(dibenzoylamino)purin-9-yl]oxolan-3-yl] benzoate 在 吡啶 、 苯磺酰胺 、 ammonium hydroxide 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三氟乙酸 作用下， 生成 2'-thiophosphoryluridylyl(3'-5')adenosine
  参考文献：
  名称：

  Kinetics and Mechanism of Facile and Selective Dephosphorylation of 2‘-Phosphorylated and 2‘-Thiophosphorylated Dinucleotides:  Neighboring 3‘−5‘ Phosphodiester Promotes 2‘-Dephosphorylation

  摘要：

  2'-phosphorylated and 2'-thiophosphorylated dinucleotides U(2'-p)pU (1) and U(2'-ps)pU (2) were found to undergo facile 2'-specific dephosphorylation at 90 degrees C in neutral aqueous solution to give UpU, and the first-order rate constants of these reactions were determined by HPLC. Particularly, U(2'-ps)pU (2, k = 1.38 +/- 0.4 x 10(-3) s(-1), t(comp) = 1 h) was cleanly dephosphorylated ca. 100 times more rapidly than U(2'-p)pU (1, k = 1.41 +/- 0.05 x 10(-5) s(-1), t(comp) = 72 h). Dephosphorylations of 1 and 2 were faster than those of thymidine 3'-phosphate (8) and thymidine 3'-thiophosphate (9), respectively. The kinetic data observed were independent of the 2'- or 3'-position of the phosphate group and the kind of base moiety. The neighboring 3'-5' phosphodiester function most probably promotes the 2'-dephosphorylation efficiently. A branched trimer, U(2'-pU)pU (3), and related compounds having a substituent on the 2'-phosphoryl group, such as U(2'-pp-biotin)pU (4) and U(2'-ps-bimane)pU (5), were rather resistant to hydrolysis. The addition of divalent metal ions (Mg2+, Mn2+, Zn2+, Ca2+, Co2+, and Cd2+) remarkably decreased the rate of 2'-de(thio)phosphorylation of 1 or 2. Among these metal ions, Zn2+ most significantly inhibited the dephosphorylation. On the contrary, trivalent metal ions considerably accelerated the 2'-de(thio)phosphorylation of 1 or 2. The mechanism of 2'-dephosphorylation in the presence and absence of various metal ions is also discussed.

  DOI：

  10.1021/jo970021k
• 作为产物：
  描述：

  N6-二苯甲酰基腺苷-2',3'-二苯甲酸酯 、 2'-O-bis[(2-cyano-1,1-dimethylethoxy)thiophosphoryl]-N³-benzoyl-5'-O-(4,4'-dimethoxytrityl)uridine 3'-(2-cyanoethyl-N,N-diisopropylphosphoramidite) 在 吡啶 、 四氮唑 、 水 、 碘 作用下， 生成 [(2R,3R,4R,5R)-2-[[[(2R,3R,4R,5R)-5-(3-benzoyl-2,4-dioxopyrimidin-1-yl)-4-bis[(1-cyano-2-methylpropan-2-yl)oxy]phosphinothioyloxy-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]oxolan-3-yl]oxy-(2-cyanoethoxy)phosphoryl]oxymethyl]-4-benzoyloxy-5-[6-(dibenzoylamino)purin-9-yl]oxolan-3-yl] benzoate
  参考文献：
  名称：

  Kinetics and Mechanism of Facile and Selective Dephosphorylation of 2‘-Phosphorylated and 2‘-Thiophosphorylated Dinucleotides:  Neighboring 3‘−5‘ Phosphodiester Promotes 2‘-Dephosphorylation

  摘要：

  2'-phosphorylated and 2'-thiophosphorylated dinucleotides U(2'-p)pU (1) and U(2'-ps)pU (2) were found to undergo facile 2'-specific dephosphorylation at 90 degrees C in neutral aqueous solution to give UpU, and the first-order rate constants of these reactions were determined by HPLC. Particularly, U(2'-ps)pU (2, k = 1.38 +/- 0.4 x 10(-3) s(-1), t(comp) = 1 h) was cleanly dephosphorylated ca. 100 times more rapidly than U(2'-p)pU (1, k = 1.41 +/- 0.05 x 10(-5) s(-1), t(comp) = 72 h). Dephosphorylations of 1 and 2 were faster than those of thymidine 3'-phosphate (8) and thymidine 3'-thiophosphate (9), respectively. The kinetic data observed were independent of the 2'- or 3'-position of the phosphate group and the kind of base moiety. The neighboring 3'-5' phosphodiester function most probably promotes the 2'-dephosphorylation efficiently. A branched trimer, U(2'-pU)pU (3), and related compounds having a substituent on the 2'-phosphoryl group, such as U(2'-pp-biotin)pU (4) and U(2'-ps-bimane)pU (5), were rather resistant to hydrolysis. The addition of divalent metal ions (Mg2+, Mn2+, Zn2+, Ca2+, Co2+, and Cd2+) remarkably decreased the rate of 2'-de(thio)phosphorylation of 1 or 2. Among these metal ions, Zn2+ most significantly inhibited the dephosphorylation. On the contrary, trivalent metal ions considerably accelerated the 2'-de(thio)phosphorylation of 1 or 2. The mechanism of 2'-dephosphorylation in the presence and absence of various metal ions is also discussed.

  DOI：

  10.1021/jo970021k

文献信息

• Kinetics and Mechanism of Facile and Selective Dephosphorylation of 2‘-Phosphorylated and 2‘-Thiophosphorylated Dinucleotides:  Neighboring 3‘−5‘ Phosphodiester Promotes 2‘-Dephosphorylation
  作者：Hiroyuki Tsuruoka、Koh-ichiroh Shohda、Takeshi Wada、Mitsuo Sekine

  DOI：10.1021/jo970021k

  日期：1997.5.1

  2'-phosphorylated and 2'-thiophosphorylated dinucleotides U(2'-p)pU (1) and U(2'-ps)pU (2) were found to undergo facile 2'-specific dephosphorylation at 90 degrees C in neutral aqueous solution to give UpU, and the first-order rate constants of these reactions were determined by HPLC. Particularly, U(2'-ps)pU (2, k = 1.38 +/- 0.4 x 10(-3) s(-1), t(comp) = 1 h) was cleanly dephosphorylated ca. 100 times more rapidly than U(2'-p)pU (1, k = 1.41 +/- 0.05 x 10(-5) s(-1), t(comp) = 72 h). Dephosphorylations of 1 and 2 were faster than those of thymidine 3'-phosphate (8) and thymidine 3'-thiophosphate (9), respectively. The kinetic data observed were independent of the 2'- or 3'-position of the phosphate group and the kind of base moiety. The neighboring 3'-5' phosphodiester function most probably promotes the 2'-dephosphorylation efficiently. A branched trimer, U(2'-pU)pU (3), and related compounds having a substituent on the 2'-phosphoryl group, such as U(2'-pp-biotin)pU (4) and U(2'-ps-bimane)pU (5), were rather resistant to hydrolysis. The addition of divalent metal ions (Mg2+, Mn2+, Zn2+, Ca2+, Co2+, and Cd2+) remarkably decreased the rate of 2'-de(thio)phosphorylation of 1 or 2. Among these metal ions, Zn2+ most significantly inhibited the dephosphorylation. On the contrary, trivalent metal ions considerably accelerated the 2'-de(thio)phosphorylation of 1 or 2. The mechanism of 2'-dephosphorylation in the presence and absence of various metal ions is also discussed.