2',3'-Dideoxy-β-D-glycero-pent-2'-enopyranosyl-N⁴-benzoylcytosine | 162934-40-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2',3'-Dideoxy-β-D-glycero-pent-2'-enopyranosyl-N⁴-benzoylcytosine
• 英文别名: N-[1-[(3S,6R)-3-hydroxy-3,6-dihydro-2H-pyran-6-yl]-2-oxopyrimidin-4-yl]benzamide
• CAS: 162934-40-9
• 化学式: C₁₆H₁₅N₃O₄
• 分子量: 313.313
• InChiKey: SXTKTSVTVUHJFL-GXTWGEPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  91.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2',3'-Dideoxy-β-D-glycero-pent-2'-enopyranosyl-N⁴-benzoylcytosine 在 咪唑 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 6.5h， 生成 N-[1-((3aS,5R,7aS)-2,2-Dimethyl-hexahydro-1,6-dioxa-2-sila-inden-5-yl)-2-oxo-1,2-dihydro-pyrimidin-4-yl]-benzamide
  参考文献：
  名称：

  3′-脱氧-3′-C-羟甲基-醛糖基戊吡喃糖基核苷的合成及其在寡核苷酸中的掺入。第二部分1。

  摘要：

  描述了使用分子内自由基CC键形成反应合成3'-脱氧-3'-C-羟甲基-醛基戊吡喃糖基核苷。该方法对于胸腺嘧啶和腺嘌呤核苷的合成提供了良好的结果，但对于胞嘧啶和鸟嘌呤核苷却没有。取决于构型（β-d-赤型或α-1-苏氨酸），腺嘌呤核苷的构象明显不同（α-d-赤型的轴向碱基部分和α-1-苏式核苷的赤道腺嘌呤碱基），其可以用高斯效应来解释。由2'，3'-dideoxy-3'-C-羟甲基-α-l-苏-戊吡喃糖基腺嘌呤构成的寡核苷酸能够与寡胸苷酸形成双链体，尽管稳定性不如天然dsDNA。

  DOI：

  10.1016/0040-4020(95)00777-6
• 作为产物：
  描述：

  环丙沙星 在 sodium methylate 作用下， 以 1,4-二氧六环 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.25h， 生成 2',3'-Dideoxy-β-D-glycero-pent-2'-enopyranosyl-N⁴-benzoylcytosine
  参考文献：
  名称：

  Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides

  摘要：

  Condensation of 3,4-bis-O-(p-nitrobenzoyl)-D-xylal with purines and pyrimidines (A, C, 6-chloropurine, G, T, U) without externally added acid catalyst leads to the 2',3'-unsaturated pentopyranosyl nucleosides in preparatively acceptable yields of both beta and alpha anomers and near complete suppression of formation of the 3'-substituted 1',2'-unsaturated regioisomers. Anomeric configurations of these analogues of nucleosides have been established for the 4'-O-deprotected derivatives by way of C-13 NMR. In all nine anomeric pairs the signals of the carbon atoms C-5' in alpha anomers are shifted upfield when compared with the corresponding signals of the beta anomers. Coupling constants J(4'5'ax) indicate pseudoaxial positions of purines in 33-40, 45, and 46. This is rationalized in terms of a pi-o*(c-1'-N-9) resonance and represents a case where aglycons occupy pseudoaxial positions via a mechanism'different than the anomeric effect. The same coupling constants of the alpha-pyrimidines 30, 32, 42, and 44 indicate H-4(0)<->H-0(4) equilibrium with a marginal preference toward the H-0(4) form, whereas the beta-pyrimidines 29, 31, 41, and 43 show a preference toward H-0(4) probably due to steric interactions.

  DOI：

  10.1021/jo00129a035

文献信息

• Synthesis of β configured 2′,3′-unsaturated pentopyranosyl nucleosides
  作者：Bodgan Doboszewski、Norbert Blaton、Piet Herdewijn

  DOI：10.1016/0040-4039(94)02466-o

  日期：1995.2

  of 3,4-di-O-p-nitrobenzoyl-D-xylal with heterocyclic bases in boiling DMF in the absence of externally added acid catalyst constitutes a convenient way to β configured 2′,3′-unsaturated pentopyranosyl nucleosides. Formation of the 3′-substituted products (without migration of a double bond) has been practically avoided.

  在没有外部添加的酸催化剂的情况下，在沸腾DMF中将3,4-二-O-硝基苯甲酰基-D-二甲苯基与杂环碱偶联，是构建β构型的2'，3'-不饱和戊吡喃糖基核苷的简便方法。实际上已经避免了形成3'-取代的产物（没有双键的迁移）。
• Synthesis of the β-2',3'-Unsaturated Pentopyranosyl Nucleosides and Their 3'-Hydroxymethyl Congeners
  作者：Bogdan Doboszewski、Norbert Blaton、Piet Herdewijn

  DOI：10.1080/15257779508012371

  日期：1995.5.1

  Fusion of the glycal 3 and purines/pyrimidines without acid catalyst provides anomeric mixtures of the 2',3'-unsaturated pentopyranosyl nucleosides 4, which have been worked out to furnish the 3'-hydroxymethyl analogues, e.g. 5.
• Easy Synthesis and Different Conformational Behavior of Purine and Pyrimidine .beta.-D-glycero-Pent-2'-enopyranosyl Nucleosides
  作者：Bogdan Doboszewski、Norbert Blaton、Piet Herdewijn

  DOI：10.1021/jo00129a035

  日期：1995.12

  Condensation of 3,4-bis-O-(p-nitrobenzoyl)-D-xylal with purines and pyrimidines (A, C, 6-chloropurine, G, T, U) without externally added acid catalyst leads to the 2',3'-unsaturated pentopyranosyl nucleosides in preparatively acceptable yields of both beta and alpha anomers and near complete suppression of formation of the 3'-substituted 1',2'-unsaturated regioisomers. Anomeric configurations of these analogues of nucleosides have been established for the 4'-O-deprotected derivatives by way of C-13 NMR. In all nine anomeric pairs the signals of the carbon atoms C-5' in alpha anomers are shifted upfield when compared with the corresponding signals of the beta anomers. Coupling constants J(4'5'ax) indicate pseudoaxial positions of purines in 33-40, 45, and 46. This is rationalized in terms of a pi-o*(c-1'-N-9) resonance and represents a case where aglycons occupy pseudoaxial positions via a mechanism'different than the anomeric effect. The same coupling constants of the alpha-pyrimidines 30, 32, 42, and 44 indicate H-4(0)<->H-0(4) equilibrium with a marginal preference toward the H-0(4) form, whereas the beta-pyrimidines 29, 31, 41, and 43 show a preference toward H-0(4) probably due to steric interactions.
• Synthesis of 3′-Deoxy-3′-C-Hydroxymethyl-aldopentopyranosyl Nucleosides and their Incorporation in Oligonucleotides. Part II 1.
  作者：Bogdan Doboszewski、Hans De Winter、Arthur Van Aerschot、Piet Herdewijn

  DOI：10.1016/0040-4020(95)00777-6

  日期：1995.11

  The synthesis of 3′-deoxy-3′-C-hydroxymethyl-aldopentopyranosyl nucleosides using an intramolecular radical C-C bond formation reaction is described. This method gives good results for the synthesis of thymine and adenine nucleosides, but not for cytosine and guanine nucleosides. Dependent on the configuration (β-d-erythro or α-l-threo), the conformation of the adenine nucleosides is clearly different

  描述了使用分子内自由基CC键形成反应合成3'-脱氧-3'-C-羟甲基-醛基戊吡喃糖基核苷。该方法对于胸腺嘧啶和腺嘌呤核苷的合成提供了良好的结果，但对于胞嘧啶和鸟嘌呤核苷却没有。取决于构型（β-d-赤型或α-1-苏氨酸），腺嘌呤核苷的构象明显不同（α-d-赤型的轴向碱基部分和α-1-苏式核苷的赤道腺嘌呤碱基），其可以用高斯效应来解释。由2'，3'-dideoxy-3'-C-羟甲基-α-l-苏-戊吡喃糖基腺嘌呤构成的寡核苷酸能够与寡胸苷酸形成双链体，尽管稳定性不如天然dsDNA。