2'-O-t-butyldimethylsilyluridine 3'-(uridine 5'-phosphate) | 120401-11-8

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - （3'->5'）-二核苷酸和类似物
• 英文名称: 2'-O-t-butyldimethylsilyluridine 3'-(uridine 5'-phosphate)
• 英文别名: [(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-(2,4-dioxopyrimidin-1-yl)-2-(hydroxymethyl)oxolan-3-yl] [(2R,3S,4R,5R)-5-(2,4-dioxopyrimidin-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl hydrogen phosphate
• CAS: 120401-11-8
• 化学式: C₂₄H₃₇N₄O₁₄PSi
• 分子量: 664.635
• InChiKey: XZNLDXPXXFUQAG-QBDYWJJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.51
• 重原子数：
  44
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  243
• 氢给体数：
  6
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2'-O-t-butyldimethylsilyluridine 3'-(uridine 5'-phosphate) 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 尿苷酰基-(3',5')-尿苷
  参考文献：
  名称：

  磷酸三酯法在溶液中使用2'-叔丁基二甲基甲硅烷基保护合成的2'-5'和3'-5'RNA六聚体AACCUU的光谱和酶促表征

  摘要：

  比较的1 H，31 P NMR和CD光谱结果以及具有相同碱基序列（AACCUU）但在核苷酸间磷酸酯键（2'–t'，3'–5'和它们的共价键是区域异构的单链RNA六聚体的酶促裂解混合）。在31P NMR结果显示这些异构体之间的局部磷酸酯主链构象存在显着差异，与3'-5'异构体，类似的DNA六聚体和共价杂合六聚体相比，2'-5'异构体表现出最大的异质性。与此相反，从2'-5'和3'-5'异构体的CD光谱中可以看出，总体的碱基-碱基堆积没有明显的差异。通过溶液相磷酸三酯化学合成所有的RNA六聚体，其中叔丁基二甲基甲硅烷基（TBDMS）作为2'-O-保护基。完全保护的低聚物通过两个步骤脱保护：（i）饱和无水MeOH = NH 3进行磷酸和氨基脱保护，（ii）TBAF去除2'-O-TBDMS基团。使用坐。MeOHNH 3（而不是水溶液。NH 3）可防止2'–3'核苷酸间磷酸酯迁移，链断裂和邻近基团

  DOI：

  10.1016/s0040-4020(01)80945-5
• 作为产物：
  描述：

  5'-O-DMTr-2'-O-TBDMS-uridine-3'-O-(2-chlorophenyl)phosphate triethylammonium salt 在 吡啶 、 N-甲基咪唑 、 二氯乙酸 、 MSNT 、 氨 作用下， 以 二氯甲烷 为溶剂， 反应 21.5h， 生成 2'-O-t-butyldimethylsilyluridine 3'-(uridine 5'-phosphate)
  参考文献：
  名称：

  磷酸三酯法在溶液中使用2'-叔丁基二甲基甲硅烷基保护合成的2'-5'和3'-5'RNA六聚体AACCUU的光谱和酶促表征

  摘要：

  比较的1 H，31 P NMR和CD光谱结果以及具有相同碱基序列（AACCUU）但在核苷酸间磷酸酯键（2'–t'，3'–5'和它们的共价键是区域异构的单链RNA六聚体的酶促裂解混合）。在31P NMR结果显示这些异构体之间的局部磷酸酯主链构象存在显着差异，与3'-5'异构体，类似的DNA六聚体和共价杂合六聚体相比，2'-5'异构体表现出最大的异质性。与此相反，从2'-5'和3'-5'异构体的CD光谱中可以看出，总体的碱基-碱基堆积没有明显的差异。通过溶液相磷酸三酯化学合成所有的RNA六聚体，其中叔丁基二甲基甲硅烷基（TBDMS）作为2'-O-保护基。完全保护的低聚物通过两个步骤脱保护：（i）饱和无水MeOH = NH 3进行磷酸和氨基脱保护，（ii）TBAF去除2'-O-TBDMS基团。使用坐。MeOHNH 3（而不是水溶液。NH 3）可防止2'–3'核苷酸间磷酸酯迁移，链断裂和邻近基团

  DOI：

  10.1016/s0040-4020(01)80945-5

文献信息

• Unprecedented Mild Acid-Catalyzed Desilylation of the 2‘-O-<i>tert</i>-Butyldimethylsilyl Group from Chemically Synthesized Oligoribonucleotide Intermediates <i>via</i> Neighboring Group Participation of the Internucleotidic Phosphate Residue
  作者：Shun-ichi Kawahara、Takeshi Wada、Mitsuo Sekine

  DOI：10.1021/ja961959i

  日期：1996.1.1

  Hydrolytic removal of the 2'-tert-butyldimethylsilyl (TBDMS) group from a 2'-O-TBDMS protected UpU dimer [U(2'-Si)pU] (1) (Si = TBDMS) and related derivatives under various acidic conditions was studied in detail. First, desilylation of 1 by use of acetic acid was examined. Consequently, we made the unprecedented discovery that cleavage of the 2'-silyl ether linkage occurred fastest at a very low concentration of acetic acid within the range of 5-10%, depending on the temperature, Formic acid could cleave the silyl ether much faster than acetic acid, but the relationship between the reaction rate and the concentration of acid was different from that of acetic acid. The use of 20-40% formic acid resulted in very effective elimination of the 2'-TBDMS group, Moreover, diluted HCl solution (pH 2.0) could cleave the Si-O bond faster than acetic acid at 30 degrees C. In contrast, the 2'-silyl group of the corresponding methylphosphonate derivative [U(2'-Si)p(Me)U] (3) was much more stable than that of 1. In the case of a diastereomeric mixture of the phosphorothioate dimer [U(2'-Si)psU] (2), a big difference in reaction rate between the Rp- and Sp-diastereomers was observed. These results strongly suggest that neighboring group participation of the 3'-5' phosphorodiester group is involved in the present acid-catalyzed 2'-desilylation. These conditions were successfully applied to the deprotection of the 2'-TBDMS group of an RNA intermediate which was chemically synthesized by the conventional phosphoramidite approach on a CPG gel.
• RNA-Synthesis Using the H-Phosphonate Approach and an Improved Protecting Group Strategy
  作者：Erik Westman、Susannah Sigurdsson、Helena Almer、Mats Thelin、Jacek Stawinski、Eriks Rozners、Roger Strömberg

  DOI：10.1080/15257779508012495

  日期：1995.5.1

  An improved version of the H-phosphonate approach to RNA-synthesis is presented and the studies that led to alterations in the protecting group strategy are discussed.