2-amino-3,7-dihydro-7-(β-D-ribofuranosyl)-5-[(trimethylsilyl)ethynyl]-4H-pyrrolo[2,3-d]pyrimidin-4-one | 873792-96-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 吡咯并嘧啶核苷和核苷酸
• 英文名称: 2-amino-3,7-dihydro-7-(β-D-ribofuranosyl)-5-[(trimethylsilyl)ethynyl]-4H-pyrrolo[2,3-d]pyrimidin-4-one
• 英文别名: 2-amino-7-[(2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]-5-(2-trimethylsilylethynyl)-3H-pyrrolo[2,3-d]pyrimidin-4-one
• CAS: 873792-96-2
• 化学式: C₁₆H₂₂N₄O₅Si
• 分子量: 378.46
• InChiKey: MSRICHSJLILPSB-SDBHATRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.85
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  142
• 氢给体数：
  5
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-amino-3,7-dihydro-7-(β-D-ribofuranosyl)-5-[(trimethylsilyl)ethynyl]-4H-pyrrolo[2,3-d]pyrimidin-4-one 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 生成 2-amino-3,7-dihydro-5-ethynyl-7-(β-D-ribofuranosyl)-4H-pyrrolo[2,3-d]pyrimidin-4-one
  参考文献：
  名称：

  有效合成的7功能7-脱氮嘌呤β-D-或β-L-核糖核苷：吡咯并[2,3-D]嘧啶与1-O-乙酰基-2,3,5-Tri-O-苄基的糖基化-D-或L-呋喃核糖

  摘要：

  描述了使用可商购的1-O-乙酰基-2,3,5-三-O-苯甲酰基-D-或L-呋喃呋喃糖酶用7-卤代7-脱氮嘌呤进行的糖基化反应。

  DOI：

  10.1080/15257770701490332
• 作为产物：
  描述：

  4-chloro-5-iodo-2-(pivaloylamino)-7-[(2,3,5-tri-O-benzoyl)-β-D-ribofuranosyl]-7H-pyrrolo[2,3-d]pyrimidine 在 四(三苯基膦)钯 sodium hydroxide 、 copper(l) iodide 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 2-amino-3,7-dihydro-7-(β-D-ribofuranosyl)-5-[(trimethylsilyl)ethynyl]-4H-pyrrolo[2,3-d]pyrimidin-4-one
  参考文献：
  名称：

  7-Functionalized 7-Deazapurine Ribonucleosides Related to 2-Aminoadenosine, Guanosine, and Xanthosine:  Glycosylation of Pyrrolo[2,3-d]pyrimidines with 1-O-Acetyl-2,3,5-tri-O-benzoyl-d-ribofuranose

  摘要：

  The Silyl-Hilbert-Johnson reaction as well as the nucleobase-anion glycosylation of a series of 7-deazapurines has been investigated, and the 7-functionalized 7-deazapurine ribonucleosides were prepared. Glycosylation of the 7-halogenated 6-chloro-2-pivaloylamino-7-deazapurines 9b-d with 1-O-acetyl2,3,5-tri-O-benzOyl-D-ribofuranose (5) gave the beta-D-nucleosides 11b-d (73-75% yield), which were transformed to a number of novel 7-halogenated 7-deazapurine ribonucleosides (2b-d, 3b-d, and 4b-d) related to guanosine, 2-aminoadenosine, and xanthosine. 7-Alkynyl derivatives (2e-i, 3e-h, or 4g) have been prepared from the corresponding 7-iodonucleosides 2d, 3d, or 4d employing the palladium-catalyzed Sonogashira cross-coupling reaction. The 7-halogenated 2-amino-7-deazapurine ribonucleosides with a reactive 6-chloro substituent (18b-d) were synthesized in an alternative way using nucleobase-anion glycosylation performed on the 7-halogenated 2-arnino-6-chloro-7-deazapurines 13b-d with 5-0-[(1,1dimethylethyl)dimethylsilyl]-2,3-O-(1-methylethylidene)-alpha-D-ribofuranosyl chloride (17). Compounds 18b-d have been converted to the nucleosides 19b-d carrying reactive substituents in the pyrimidine moiety. Conformational analysis of selected nucleosides on the basis of proton coupling constants and using the program PSEUROT showed that these ribonucleosides exist in a preferred S conformation in solution.

  DOI：

  10.1021/jo0516640

文献信息

• Enzymatic synthesis of base-modified RNA by T7 RNA polymerase. A systematic study and comparison of 5-substituted pyrimidine and 7-substituted 7-deazapurine nucleoside triphosphates as substrates
  作者：Nemanja Milisavljevič、Pavla Perlíková、Radek Pohl、Michal Hocek

  DOI：10.1039/c8ob01498a

  日期：——

  initiator needed to be used to obtain efficient RNA synthesis. The T7 RNA polymerase synthesis of modified RNA can be very efficiently used for synthesis of modified RNA but the method has constraints in the sequence of the first three nucleotides of the transcript, which must contain a non-modified G in the +1 position.

  我们通过核苷的交叉偶联反应，随后的三磷酸化反应或通过卤化的直接交叉偶联反应，合成了一个小库，该库包含十八个带有甲基，乙炔基，苯基，苯并呋喃基或二苯并呋喃基的5-取代的嘧啶或7-取代的7-脱氮嘌呤核苷三磷酸核苷三磷酸。我们系统地研究了修饰对T7 RNA聚合酶催化的修饰RNA合成效率的影响，发现修饰较小的修饰ATP，UTP和CTP类似物是RNA合成的良好底物和基石，即使在困难的序列中掺入了多个修饰的核苷酸。ATP和GTP的大体积二苯并呋喃基衍生物不是RNA聚合酶的底物。对于修饰的GTP类似物，需要使用特殊的启动子和GMP作为引发剂的改良程序，才能获得有效的RNA合成。修饰的RNA的T7 RNA聚合酶合成可以非常有效地用于修饰的RNA的合成，但是该方法在转录本的前三个核苷酸的序列中有限制，该转录本的前三个核苷酸必须在+1位包含一个未修饰的G。
• An Efficient Synthesis Of 7-Functionalized 7-Deazapurine β-D- Or β-L-Ribonucleosides: Glycosylation Of Pyrrolo[2,3-D]Pyrimidines With 1-O-Acetyl-2,3,5-Tri-O-Benzoyl-D-Or L-Ribofuranose
  作者：Xiaohua Peng、Frank Seela

  DOI：10.1080/15257770701490332

  日期：2007.11.26

  The glycosylation reaction performed with 7-halogenated 7-deazapurines employing commercially available 1-O-acetyl-2,3,5-tri-O-benzoyl-D- or L-ribofuranoses is described.

  描述了使用可商购的1-O-乙酰基-2,3,5-三-O-苯甲酰基-D-或L-呋喃呋喃糖酶用7-卤代7-脱氮嘌呤进行的糖基化反应。
• 7-Functionalized 7-Deazapurine Ribonucleosides Related to 2-Aminoadenosine, Guanosine, and Xanthosine:  Glycosylation of Pyrrolo[2,3-<i>d</i>]pyrimidines with 1-<i>O</i>-Acetyl-2,3,5-tri-<i>O</i>-benzoyl-<scp>d</scp>-ribofuranose
  作者：Frank Seela、Xiaohua Peng

  DOI：10.1021/jo0516640

  日期：2006.1.1

  The Silyl-Hilbert-Johnson reaction as well as the nucleobase-anion glycosylation of a series of 7-deazapurines has been investigated, and the 7-functionalized 7-deazapurine ribonucleosides were prepared. Glycosylation of the 7-halogenated 6-chloro-2-pivaloylamino-7-deazapurines 9b-d with 1-O-acetyl2,3,5-tri-O-benzOyl-D-ribofuranose (5) gave the beta-D-nucleosides 11b-d (73-75% yield), which were transformed to a number of novel 7-halogenated 7-deazapurine ribonucleosides (2b-d, 3b-d, and 4b-d) related to guanosine, 2-aminoadenosine, and xanthosine. 7-Alkynyl derivatives (2e-i, 3e-h, or 4g) have been prepared from the corresponding 7-iodonucleosides 2d, 3d, or 4d employing the palladium-catalyzed Sonogashira cross-coupling reaction. The 7-halogenated 2-amino-7-deazapurine ribonucleosides with a reactive 6-chloro substituent (18b-d) were synthesized in an alternative way using nucleobase-anion glycosylation performed on the 7-halogenated 2-arnino-6-chloro-7-deazapurines 13b-d with 5-0-[(1,1dimethylethyl)dimethylsilyl]-2,3-O-(1-methylethylidene)-alpha-D-ribofuranosyl chloride (17). Compounds 18b-d have been converted to the nucleosides 19b-d carrying reactive substituents in the pyrimidine moiety. Conformational analysis of selected nucleosides on the basis of proton coupling constants and using the program PSEUROT showed that these ribonucleosides exist in a preferred S conformation in solution.