9-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-1-[(3aS,4R,6R,6aR)-6-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]-8-bromopurin-6-one | 203249-44-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 9-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-1-[(3aS,4R,6R,6aR)-6-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]-8-bromopurin-6-one
• CAS: 203249-44-9
• 化学式: C₃₆H₆₁BrN₄O₈Si₂
• 分子量: 813.977
• InChiKey: ZVCXCIFCRZLRJU-BFRAKZNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.53
• 重原子数：
  51
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  9-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-1-[(3aS,4R,6R,6aR)-6-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]-8-bromopurin-6-one 在 四丁基氟化铵 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  细胞内Ca（2+）动员腺嘌呤核苷酸。腺苷A的环状ADP-碳环核糖和C-糖苷类似物的合成及其生物学活性。

  摘要：

  我们设计了新颖的Ca（2+）动员嘌呤核苷酸，环ADP-碳环核糖4，其肌苷同源物5和C-糖苷腺苷A6。在合成cADPR类似物时，分子内缩合形成焦磷酸酯键应为关键步骤。我们开发了一种通过用I2或AgNO3活化苯硫代磷酸酯基团来形成分子内焦磷酸酯键的有效方法。使用该方法，我们合成了目标化合物4和5。使用暂时的硅链自由基偶联反应来构建（3'alpha，1“ alpha）-C，可以合成腺磷素A的C-糖苷类似物6。 -糖苷结构为关键步骤。

  DOI：

  10.1081/ncn-100002320
• 作为产物：
  描述：

  8-溴-2',3'-O-(1-甲基乙亚基)-肌苷 在 咪唑 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 14.33h， 生成 9-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-1-[(3aS,4R,6R,6aR)-6-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]-8-bromopurin-6-one
  参考文献：
  名称：

  Nucleosides and Nucleotides. 173. Synthesis of Cyclic IDP-carbocyclic-ribose, a Stable Mimic of Cyclic ADP-ribose. Significant Facilitation of the Intramolecular Condensation Reaction of N-1-(Carbocyclic-ribosyl)inosine 5‘,6‘‘-Diphosphate Derivatives by an 8-Bromo-Substitution at the Hypoxanthine Moiety

  摘要：

  Cyclic ADP-ribose (cADPR, 1) is a general mediator involved in cellular Ca2+ signaling. However, both the biological and chemical instability of cADPR limit studies on its physiological role. We designed cyclic ADP-carbocyclic-ribose (3) and its inosine congener 4 as stable mimics of cADPR and successfully synthesized 4. Starting with cyclopentadiene, the optically active carbocyclic unit 8 was constructed via enzymatic optical resolution. S(N)2 reactions of 8 with inosine derivative 7 and the 8-bromoinosine derivative 25 gave the N-1-substituted derivatives 6 and 26, which were converted to the corresponding diphosphate derivatives 5 and 22. The intramolecular condensation reactions between the two phosphate groups of 5 and 22 were investigated, Although the reaction with inosine derivative 5 did not produce any of the cyclization product 20, treatment of the corresponding 8-bromoinosine derivative 22 with EDC gave the desired intramolecular condensation product 29 in 23% yield. Thus, the significant effect of the 8-bromo group at the hypoxanthine moiety in facilitating the key intramolecular condensation reaction between the phosphate groups of the substrate 22 was recognized. This is possibly due to conformational restriction of the molecule in a syn-form around its glycosyl linkage. The 8-bromo and isopropylidene groups were removed in succession to give the target compound 4. This is the first total synthesis of this type of cyclic nucleotide.

  DOI：

  10.1021/jo9717797

文献信息

• Alternative synthesis of cyclic IDP-carbocyclic ribose. Efficient cyclization of an 8-bromo-N1-[5-(phosphoryl)carbocyclic-ribosyl]inosine 5′-phenylthiophosphate derivative mediated by iodine
  作者：Masayoshi Fukuoka、Satoshi Shuto、Noriaki Minakawa、Yoshihito Ueno、Akira Matsuda

  DOI：10.1016/s0040-4039(99)00977-6

  日期：1999.7

  An efficient synthesis of cyclic IDP-carbocyclic-ribose, as a stable mimic for cyclic ADP-ribose, was achieved. N-1-Carbocyclic-ribosylinosine derivative 15, prepared from N-1-(2,4-dinitrophenyl)inosine derivative 10 and an optically active carbocyclic amine 11, was converted to 8-bromo-N-1-carbocyclic-ribosylinosine bis-phosphate derivative 20. Treatment of 20 with I-2 in the presence of molecular sieves in pyridine gave the desired cyclic product 8 quantitatively, which was deprotected and reductively debrominated to give the target cyclic IDP-carbocyclic ribose (3). (C) 1999 Elsevier Science Ltd. All rights reserved.