2-amino-6-methoxy-9-<2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuranosyl>purine | 128790-73-8

• 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: 2-amino-6-methoxy-9-<2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuranosyl>purine
• 英文别名: 3',5'-bis-O-(tert-butyldimethylsilyl)-O⁶-methyl-2'-deoxyguanosine；O⁶-methyl-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine；O⁶-methyl-3',5'-bis(O-tert-butyldimethylsilyl)-2'-deoxyguanosine；3',5'-di-O-(tert-butyldimethylsilyl)-O6-methyl-2'-deoxyguanosine；2-amino-6-methoxy-9-[2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-Beta-D-erythro-pentofuranosyl]purine；2-amino-6-methoxy-9-[2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuranosyl]purine；9-[(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-methoxypurin-2-amine
• CAS: 128790-73-8
• 化学式: C₂₃H₄₃N₅O₄Si₂
• 分子量: 509.797
• InChiKey: LEDZWXXTAUNAPL-GVDBMIGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.12
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  溴苯 、 2-amino-6-methoxy-9-<2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuranosyl>purine 在 palladium diacetate 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以89%的产率得到3',5'-bis-O-(tert-butyldimethylsilyl)-O⁶-methyl-N²-phenyl-2'-deoxyguanosine
  参考文献：
  名称：

  Pd−Xantphos-Catalyzed Direct Arylation of Nucleosides

  摘要：

  Direct arylation of the exocyclic amino groups of nucleosides represents a simple approach to N-aryl nucleoside derivatives. To date, one limitation has been that only electron-deficient aryl bromides and triflates possessed adequate reactivity for efficient, direct N-arylation of nucleosides. We demonstrate herein that Pd-Xantphos catalytic systems lead to successful N-arylation of suitably protected 2'-deoxyadenosine and 2'-deoxyguanosine with a wide range of aryl bromides.

  DOI：

  10.1021/ol0619516
• 作为产物：
  描述：

  3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine 在 caesium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 5.0h， 生成 2-amino-6-methoxy-9-<2-deoxy-3,5-bis-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuranosyl>purine
  参考文献：
  名称：

  一种简单的鸟嘌呤核苷 C-6 修饰方法†

  摘要：

  在 C-6 位置引入各种取代基的简便方法 鸟苷 和 2'-脱氧鸟苷被报道。在简单的 1 步转化中，叔丁基二甲基甲硅烷基保护的鸟苷和2'-脱氧鸟苷通过与 1 H-苯并三唑-1-基氧基-三（二甲氨基）鏻六氟磷酸盐 (BOP)反应转化为O 6 -(苯并三唑-1-基) 衍生物和1,8-二氮杂双环[5.4.0]undec-7ene(DBU)。容易分离、稳定和可储存的O 6 -(苯并三唑-1-基)鸟苷衍生物在适当条件下暴露于一系列亲核试剂后，以良好的产率得到 C-6 修饰的 2-氨基嘌呤核苷类似物。

  DOI：

  10.1039/b905298d

文献信息

• Synthesis of 6-substituted 2′-deoxyguanosine derivatives using trifluoroacetic anhydride in pyridine
  作者：Fathi Reza、Goswami Bhaswati、Kung Pei-Pei、Barbara L. Gaffney、Roger A. Jones

  DOI：10.1016/s0040-4039(00)94543-x

  日期：1990.1

  Trifluoroacetic anhydride at 0° C reacts with a pyridine suspension of deoxyguanosine to generate a polar intermediate, presumably the corresponding 6-pyridyl derivative. The reaction is complete in less than 15 minutes, and is not accompanied by degradation. From this intermediate a variety of 6-substituted deoxyguanosine derivatives can be obtained, some in excellent yields.

  0℃下的三氟乙酸酐与脱氧鸟苷的吡啶悬浮液反应，生成极性中间体，可能是相应的6-吡啶基衍生物。反应在不到15分钟的时间内完成，并且没有降解。从该中间体可以得到多种6-取代的脱氧鸟苷衍生物，其中一些具有优异的收率。
• One-Pot Etherification of Purine Nucleosides and Pyrimidines
  作者：Hari Prasad Kokatla、Mahesh K. Lakshman

  DOI：10.1021/ol101655h

  日期：2010.10.15

  A one-pot synthesis of ethers derived from inosine, guanosine, 2'-deoxyguanosine, and pyrimidinones is described Exposure of the heterocycle to 1H-benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP) and Cs2CO3 produces a reactive intermediate, which is converted to the desired ether by subsequent addition of an appropriate alcohol or phenol and Cs2CO3. Although rapid formation of HMPA from BOP can occur in the presence of an alcohol and base, as demonstrated by the reaction with methanol, under appropriate conditions these heteroaryl ethers can be efficiently synthesized
• Facile Synthesis of <i>O</i>⁶-Alkyl-, <i>O</i>⁶-Aryl-, and Diaminopurine Nucleosides from 2‘-Deoxyguanosine
  作者：Mahesh K. Lakshman、Felix N. Ngassa、John C. Keeler、Yen Q. V. Dinh、John H. Hilmer、Larry M. Russon

  DOI：10.1021/ol005564m

  日期：2000.4.1

  [GRAPHICS]The 3',5'-bis-O-TBDMS derivative of 2'-deoxyguanosine can be converted to its O-6-alkyl and O-6-aryl ethers as well as to N-6-substituted diaminopurine nucleosides in two simple steps. Also described is a novel, nonaqueous, one-step O-6-desulfonylation method that leads to deprotection of the carbonyl moiety of 2'-deoxyguanosine.
• Direct Synthesis of 8-Fluoro Purine Nucleosides via Metalation−Fluorination
  作者：Arun K. Ghosh、Pallavi Lagisetty、Barbara Zajc

  DOI：10.1021/jo071121l

  日期：2007.10.1

  A straightforward access to protected 8-fluoro nucleosides via metal ation - electrophilic fluorination under heterogeneous reaction conditions is reported. This is the first synthesis of 8-fluoro-2(')-deoxyribonucleoside derivatives. Phenylsulfonyl substituted nucleosides are accompanying byproducts, possibly indicating a competing radical process. Higher yields of 8-fluoro derivatives were obtained with 2(')-deoxyribonucleosides, as compared to ribonucleosides. Deprotection of the hydroxyl groups leading to 8-fluoro-2(')deoxyadenosine using TASF in methylene chloride demonstrates the compatibility of desilylation with 8-fluoro substituted nucleosides. NMR data indicate a syn conformation of the 8-fluoro derivatives.
• Pd−Xantphos-Catalyzed Direct Arylation of Nucleosides
  作者：Felix N. Ngassa、Kyle A. DeKorver、Theothora S. Melistas、Edmund A.-H. Yeh、Mahesh K. Lakshman

  DOI：10.1021/ol0619516

  日期：2006.9.1

  Direct arylation of the exocyclic amino groups of nucleosides represents a simple approach to N-aryl nucleoside derivatives. To date, one limitation has been that only electron-deficient aryl bromides and triflates possessed adequate reactivity for efficient, direct N-arylation of nucleosides. We demonstrate herein that Pd-Xantphos catalytic systems lead to successful N-arylation of suitably protected 2'-deoxyadenosine and 2'-deoxyguanosine with a wide range of aryl bromides.