2',3'-bis-O-(tert-butyldimethylsilyl)uridin-5'-yl hydrogen phosphonate,triethylammonium salt | 143294-18-2

• 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: 2',3'-bis-O-(tert-butyldimethylsilyl)uridin-5'-yl hydrogen phosphonate,triethylammonium salt
• 英文别名: triethylammonium salt of 2',5'-bis-O-(tert-butyldimethylsilyl)-uridine 5'-hydrogenphosphonate；[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-(2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxyphosphinic acid;N,N-diethylethanamine
• CAS: 143294-18-2
• 化学式: C₆H₁₅N*C₂₁H₄₁N₂O₈PSi₂
• 分子量: 637.902
• InChiKey: IKIBMDUUWJYQCH-VRGWARIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  41.0
• 可旋转键数：
  11.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  132.32
• 氢给体数：
  2.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2',3'-bis-O-(tert-butyldimethylsilyl)uridin-5'-yl hydrogen phosphonate,triethylammonium salt 在 三甲基乙酰氯 、 sulfur 作用下， 以 吡啶 为溶剂， 反应 3.0h， 生成 C₆₆H₁₀₂N₄O₁₅PSSi₅^(1-)
  参考文献：
  名称：

  Synthesis of diribonucleoside phosphorothioates via stereospecific sulfuration of H-phosphonate diesters

  摘要：

  Sulfurization of diribonucleoside H-phosphonates with elemental sulfur was found to be a stereospecific reaction. With this finding as the basis, an efficient method for the preparation of stereochemically homogeneous diribonucleoside phosphorothioates has been developed. The procedure consists of the synthesis and separation of the diastereomeric (R(p) and S(p)) pairs of the corresponding H-phosphonate diesters, followed by their stereospecific sulfurization and a single deprotection step using fluoride ion. The methodology has been used in synthesis of eight diribonucleoside phosphorothioates (four pairs of R(p) and S(p) diastereomers).

  DOI：

  10.1021/jo00049a022
• 作为产物：
  描述：

  三乙基碳酸氢铵缓冲液 、 2',3'-bis-O-(tert-butyldimethylsilyl)uridine 在 亚磷酸 、 三甲基乙酰氯 作用下， 以 吡啶 为溶剂， 反应 3.0h， 以80%的产率得到2',3'-bis-O-(tert-butyldimethylsilyl)uridin-5'-yl hydrogen phosphonate,triethylammonium salt
  参考文献：
  名称：

  Synthesis of diribonucleoside phosphorothioates via stereospecific sulfuration of H-phosphonate diesters

  摘要：

  Sulfurization of diribonucleoside H-phosphonates with elemental sulfur was found to be a stereospecific reaction. With this finding as the basis, an efficient method for the preparation of stereochemically homogeneous diribonucleoside phosphorothioates has been developed. The procedure consists of the synthesis and separation of the diastereomeric (R(p) and S(p)) pairs of the corresponding H-phosphonate diesters, followed by their stereospecific sulfurization and a single deprotection step using fluoride ion. The methodology has been used in synthesis of eight diribonucleoside phosphorothioates (four pairs of R(p) and S(p) diastereomers).

  DOI：

  10.1021/jo00049a022

文献信息

• Hydrolytic Reactions of Diribonucleoside 3‘,5‘-(3‘-<i>N</i>-Phosphoramidates):  Kinetics and Mechanisms for the P−O and P−N Bond Cleavage of 3‘-Amino-3‘-deoxyuridylyl-3‘,5‘-uridine
  作者：Mikko Ora、Kati Mattila、Tuomas Lönnberg、Mikko Oivanen、Harri Lönnberg

  DOI：10.1021/ja027499c

  日期：2002.12.1

  Hydrolytic reactions of 3'-amino-3'-deoxyuridylyl-3',5'-uridine (2a), an analogue of uridylyl-3',5'-uridine having the 3'-bridging oxygen replaced with nitrogen, have been followed by RP HPLC over a wide pH range. The only reaction taking place under alkaline conditions (pH > 9) is hydroxide ion-catalyzed hydrolysis (first-order in [OH(-)]) to a mixture of 3'-amino-3'-deoxyuridine 3'-phosphoramidate (7)

  3'-amino-3'-deoxyuridylyl-3',5'-uridine (2a) 的水解反应是 3'-桥接氧被氮取代的 uridylyl-3',5'-尿苷的类似物。通过 RP HPLC 在很宽的 pH 范围内。在碱性条件下（pH > 9）发生的唯一反应是氢氧根离子催化水解（在 [OH(-)] 中的一级）生成 3'-氨基-3'-脱氧尿苷 3'-氨基磷酸酯的混合物 (7 ) 和尿苷 (4)。反应进行时没有可检测到的任何中间体的积累。在 pH 6-8 时，3'-氨基-3'-脱氧尿苷 2'-磷酸 (3) 的形成与 pH 无关，与碱催化裂解竞争。然而，3 和特别是 7 在这些条件下都相当迅速地去磷酸化为 3'-氨基-3'-脱氧尿苷 (5)。在所有的可能性，3 和 7 都是通过 2'-羟基官能团对磷原子的分子内亲核攻击形成的，产生类似正膦的中间态或过渡态。在中等酸性条件下（pH 2-6），主要反应是酸催化的