N⁶-benzoyl-2',3'-O-isopropylidene-5'-O-(triethylsilyl)adenosine | 292642-43-4

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: N⁶-benzoyl-2',3'-O-isopropylidene-5'-O-(triethylsilyl)adenosine
• 英文别名: N-[9-[(3aR,4R,6R,6aR)-2,2-dimethyl-6-(triethylsilyloxymethyl)-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]purin-6-yl]benzamide
• CAS: 292642-43-4
• 化学式: C₂₆H₃₅N₅O₅Si
• 分子量: 525.68
• InChiKey: PNCNSYUOULOUPN-GUQHISFFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N⁶-benzoyl-2',3'-O-isopropylidene-5'-O-(triethylsilyl)adenosine 在 palladium on activated charcoal 、 tris(dibenzylideneacetone)dipalladium (0) copper(l) iodide 、 对甲苯磺酰叠氮 、 C₅H₁₁ONO 、 P(fur)3 、 氢气 、 碘 、 potassium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 三乙胺 为溶剂， 反应 12.25h， 生成 N⁶-benzoyl-2',3'-O-isopropylidene-5'-O-(triethylsilyl)adenosin-8-yl-(8->7)-8-amino-N⁶-benzoyl-9-[6,7-dideoxy-2,3-O-isopropylidene-5-O-(triethylsilyl)-β-D-allo-hept-6-ynofuranosyl]adenine
  参考文献：
  名称：

  含核碱基主链的寡核苷，第 4 部分，乙炔二基连接的腺苷四聚体的收敛合成

  摘要：

  Deprotection of the tetramer 24, obtained by coupling the iodinated dimer 18 with the alkyne 23 gave the 8',5-ethynediyl-linked adenosine-derived tetramer 27 (Scheme 3). As direct iodination of C(5')-ethynylated adenosine derivatives failed, we prepared 18 via the 8-amino derivative 17 that was available by coupling the imine 15 with the iodide 7; 15, in its turn, was obtained from the 8-chloro derivative 12 via the 4-methoxybenzylamine 14 (Scheme 2). This method for the introduction of the S-iodo substituent was worked out with the N-benzoyladenosine 1 that was transformed into the azide 2 by lithiation and treatment with tosyl azide (Scheme I). Reduction of 2 led to the amine 3 that was transformed into 7 I,3-Dipolar cycloaddition of 3 and (trimethylsilyl)acetylene gave 6. The 8-substituted derivatives 4a-d were prepared similarly to 2, but could not be transformed into 7 The known chloride 8 was transformed into the iodide 11 via the amines 9 and 10. The amines 3, 10, and 16 form more or less completely persistent intramolecular C(8)N-H . . . O(5') H-bonds, while the dimeric amine 17 forms a ca. 50% persistent H-bond. There is no UV evidence for a base-base interaction in the protected and deprotected dimers and tetramers.

  DOI：

  10.1002/1522-2675(20001220)83:12<3229::aid-hlca3229>3.0.co;2-s
• 作为产物：
  描述：

  三乙基氯硅烷 、 N6-苯甲酰基-2',3'-O-异丙亚基腺苷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 以97%的产率得到N⁶-benzoyl-2',3'-O-isopropylidene-5'-O-(triethylsilyl)adenosine
  参考文献：
  名称：

  含核碱基主链的寡核苷，第 2 部分，腺苷衍生单体的合成和结构测定

  摘要：

  描述了新寡核苷的腺苷衍生单体结构单元的合成和结构测定。将 Me3Si-乙炔化物添加到由已知的部分保护的腺苷 1 衍生的醛中会产生差向异构的炔丙醇 2 和 3，它们被氧化成相同的酮 4，而甲硅烷基化和去保护会产生 7 和 9（方案 1）。在炔丙基甲硅烷基醚 10 和 11 的 C(8) 处引入 I 取代基并不令人满意。因此，被保护的腺苷 12 通过去质子化和用 PhSO2Cl 处理以高产率转化为 8-氯衍生物 13；以类似的方式获得碘化物15（方案2）。8-Cl 和 8-I 衍生物 13 和 15 分别转化为炔丙醇 17、18、25 和 26（方案 3）。炔丙基衍生物 2、10、17, 19, 23, 25, 27是相关的，它们的(5'R)构型是根据脱水核苷19的NOE确定的；类似地，3、11、18、20、24、26 和 28 的相关性以及 20 的 NOE 证明了它们的 (5'S) 构型。

  DOI：

  10.1002/1522-2675(20000705)83:7<1331::aid-hlca1331>3.0.co;2-z

文献信息

• Oligonucleosides with a Nucleobase-Including Backbone, Part 4, A Convergent Synthesis of Ethynediyl-Linked Adenosine Tetramers
  作者：Hiroki Gunji、Andrea Vasella

  DOI：10.1002/1522-2675(20001220)83:12<3229::aid-hlca3229>3.0.co;2-s

  日期：2000.12.20

  Deprotection of the tetramer 24, obtained by coupling the iodinated dimer 18 with the alkyne 23 gave the 8',5-ethynediyl-linked adenosine-derived tetramer 27 (Scheme 3). As direct iodination of C(5')-ethynylated adenosine derivatives failed, we prepared 18 via the 8-amino derivative 17 that was available by coupling the imine 15 with the iodide 7; 15, in its turn, was obtained from the 8-chloro derivative 12 via the 4-methoxybenzylamine 14 (Scheme 2). This method for the introduction of the S-iodo substituent was worked out with the N-benzoyladenosine 1 that was transformed into the azide 2 by lithiation and treatment with tosyl azide (Scheme I). Reduction of 2 led to the amine 3 that was transformed into 7 I,3-Dipolar cycloaddition of 3 and (trimethylsilyl)acetylene gave 6. The 8-substituted derivatives 4a-d were prepared similarly to 2, but could not be transformed into 7 The known chloride 8 was transformed into the iodide 11 via the amines 9 and 10. The amines 3, 10, and 16 form more or less completely persistent intramolecular C(8)N-H . . . O(5') H-bonds, while the dimeric amine 17 forms a ca. 50% persistent H-bond. There is no UV evidence for a base-base interaction in the protected and deprotected dimers and tetramers.
• Oligonucleosides with a Nucleobase-Including Backbone, Part 2, Synthesis and Structure Determination of Adenosine-Derived Monomers
  作者：Hiroki Gunji、Andrea Vasella

  DOI：10.1002/1522-2675(20000705)83:7<1331::aid-hlca1331>3.0.co;2-z

  日期：2000.7.5

  I substituent at C(8) of the propargylic silyl ethers 10 and 11 was not satisfactory. The protected adenosine 12 was, therefore, transformed in high yield into the 8-chloro derivative 13 by deprotonation and treatment with PhSO2Cl; the iodide 15 was obtained in a similar way (Scheme 2). The 8-Cl and the 8-I derivatives 13 and 15 were transformed into the propargylic alcohols 17, 18, 25, and 26, respectively

  描述了新寡核苷的腺苷衍生单体结构单元的合成和结构测定。将 Me3Si-乙炔化物添加到由已知的部分保护的腺苷 1 衍生的醛中会产生差向异构的炔丙醇 2 和 3，它们被氧化成相同的酮 4，而甲硅烷基化和去保护会产生 7 和 9（方案 1）。在炔丙基甲硅烷基醚 10 和 11 的 C(8) 处引入 I 取代基并不令人满意。因此，被保护的腺苷 12 通过去质子化和用 PhSO2Cl 处理以高产率转化为 8-氯衍生物 13；以类似的方式获得碘化物15（方案2）。8-Cl 和 8-I 衍生物 13 和 15 分别转化为炔丙醇 17、18、25 和 26（方案 3）。炔丙基衍生物 2、10、17, 19, 23, 25, 27是相关的，它们的(5'R)构型是根据脱水核苷19的NOE确定的；类似地，3、11、18、20、24、26 和 28 的相关性以及 20 的 NOE 证明了它们的 (5'S) 构型。