{{(2R,3S,5R)-5-(4-bromophenyl)-2-{[(tert-butyldimethylsilyl)oxy]methyl}tetrahydrofuran-3-yl}oxy}(tert-butyl)dimethylsilane | 912818-30-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: {{(2R,3S,5R)-5-(4-bromophenyl)-2-{[(tert-butyldimethylsilyl)oxy]methyl}tetrahydrofuran-3-yl}oxy}(tert-butyl)dimethylsilane
• 英文别名: 4-(3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxy-β-D-ribofuranosyl)-1-bromobenzene；1β-(4-bromophenyl)-1,2-dideoxy-3,5-di-O-(tert-butyldimethylsilyl)-D-ribofuranose；[(2R,3S,5R)-5-(4-bromophenyl)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-3-yl]oxy-tert-butyl-dimethylsilane
• CAS: 912818-30-5
• 化学式: C₂₃H₄₁BrO₃Si₂
• 分子量: 501.652
• InChiKey: CJFMEELHOSCNKM-QHAWAJNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.69
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  {{(2R,3S,5R)-5-(4-bromophenyl)-2-{[(tert-butyldimethylsilyl)oxy]methyl}tetrahydrofuran-3-yl}oxy}(tert-butyl)dimethylsilane 在 palladium diacetate 吡啶 、 4-二甲氨基吡啶 、 potassium fluoride 、 tert-butyl-ammonium fluoride 、 potassium carbonate 、 溶剂黄146 、 2-(二叔丁基膦)联苯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 32.0h， 生成 1,2-dideoxy-1β-[4-(4-methoxyphenyl)phenyl]-D-ribofuranose
  参考文献：
  名称：

  Synthesis of functionalized biphenyl-C-nucleosides and their incorporation into oligodeoxynucleotides

  摘要：

  We describe the synthesis of eight novel C-nucleosides in which the nucleobases are replaced by biphenyl residues that carry one or two electron donor (-OCH3,-NH2) or acceptor (-NO2) functional groups in the distal ring. These C-nucleosides were synthesized convergently and in high yields from a common bromophenyl-C-nucleoside precursor via Suzuki coupling with the respective boronic acids or esters. These nucleosides were subsequently converted into the corresponding phosphoramidite building blocks and efficiently incorporated into oligodeoxynucleotides by standard phosphoramidite chemistry. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2006.05.072
• 作为产物：
  描述：

  2-deoxy-D-ribose 在 咪唑 、 三乙基硅烷 、 正丁基锂 、 三氟化硼乙醚 、 溴 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 143.5h， 生成 {{(2R,3S,5R)-5-(4-bromophenyl)-2-{[(tert-butyldimethylsilyl)oxy]methyl}tetrahydrofuran-3-yl}oxy}(tert-butyl)dimethylsilane
  参考文献：
  名称：

  Synthesis of functionalized biphenyl-C-nucleosides and their incorporation into oligodeoxynucleotides

  摘要：

  We describe the synthesis of eight novel C-nucleosides in which the nucleobases are replaced by biphenyl residues that carry one or two electron donor (-OCH3,-NH2) or acceptor (-NO2) functional groups in the distal ring. These C-nucleosides were synthesized convergently and in high yields from a common bromophenyl-C-nucleoside precursor via Suzuki coupling with the respective boronic acids or esters. These nucleosides were subsequently converted into the corresponding phosphoramidite building blocks and efficiently incorporated into oligodeoxynucleotides by standard phosphoramidite chemistry. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2006.05.072

文献信息

• Modular Synthesis of 4-Aryl- and 4-Amino-Substituted Benzene <i>C</i>-2′-Deoxyribonucleosides
  作者：Michal Hocek、Nicolas Joubert、Milan Urban、Radek Pohl

  DOI：10.1055/s-2008-1067038

  日期：——

  A modular methodology for the syntheses of various 4-substituted-phenyl C-2′-deoxyribonucleosides has been developed. Coupling of toluoylated halogenose 1 with 4-bromophenylmagnesium bromide afforded the desired bis(toluoyl)-protected 1β-(4-bromophenyl)-1,2-dideoxyribofuranose 2a, which was deprotected under Zemplen conditions to give the unprotected 1β-(4-bromophenyl)-1,2-dideoxyribofuranose 3, and reprotected to give the bis(tert-butyldimethylsilyl)-protected 1β-(4-bromophenyl)-1,2-dideoxyribofuranose 4. Alternatively, addition of 1-lithio-4-bromobenzene on tert-butyldimethylsilyl-protected lactone 5, followed by reduction of the hemiketal 6, also gave bis(tert-butyldimethylsilyl)-protected bromophenyl nucleoside 4. Intermediates 2a and 4 were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, and C-H activation to give 1β-[4-(aryl-, alkyl-, or amino)phenyl]-1,2-dideoxyribofuranoses 8a-n after deprotection. Finally, other types of 4-arylphenyl C-nucleosides 8o-u were prepared directly by aqueous-phase Suzuki cross-coupling reactions of unprotected 3 with boronic acids under microwave irradiation.

  已开发出用于合成各种 4-取代-苯基 C-2'-脱氧核糖核苷的模块化方法。甲苯酰化卤糖 1 与 4-溴苯基溴化镁的偶联提供了所需的双（甲苯酰）保护的 1β-(4-溴苯基)-1,2-二脱氧呋喃核糖 2a，其在 Zemplen 条件下脱保护，得到未保护的 1β-(4-溴苯基) )-1,2-二脱氧呋喃核糖 3，并重新保护以得到双(叔丁基二甲基甲硅烷基)-保护的 1β-(4-溴苯基)-1,2-二脱氧呋喃核糖 4。或者，在叔上添加 1-锂-4-溴苯-丁基二甲基甲硅烷基保护的内酯5，随后还原半缩酮6，也得到双(叔丁基二甲基甲硅烷基)保护的溴苯基核苷4。然后中间体2a和4进行一系列钯催化的交叉偶联反应、胺化、和 C-H 活化以给出 1β-[4-(芳基-、烷基-或氨基)苯基]-1,2-二脱氧呋喃核糖 8a-n 脱保护后。最后，在微波辐射下，通过未保护的3与硼酸的水相Suzuki交叉偶联反应直接制备了其他类型的4-芳基苯基C-核苷8o-u。
• Synthesis of Phenol and Pyridone C-Ribo- and 2′-Deoxyribonucleosides by Palladium-Catalyzed Hydroxylations of Haloaryl C-Nucleosides
  作者：Michal Hocek、Martin Štefko

  DOI：10.1055/s-0030-1258318

  日期：2010.12

  Phenol and pyridone C-nucleosides in both ribo- and deoxyribo series were prepared by palladium-catalyzed hydroxylations reactions from the corresponding TBS-protected bromophenyl and bromo- or chloropyridyl C-nucleosides using Buchwald-type ligand under mild conditions. Partial or complete desilylation of 5′-OH was observed in some cases. Free nucleosides (7 examples) were obtained in good overall

  核糖和脱氧核糖系列中的苯酚和吡啶酮C-核苷是由钯催化的羟基化反应，由相应的TBS保护的溴苯基和溴或氯吡啶基C-核苷在温和条件下使用Buchwald型配体制备的。在某些情况下，观察到5'-OH的部分或完全甲硅烷基化。游离核苷（7个实施例）在由TBS保护基团用Et切割好的总产率得到3 N˙3HF。 C-核苷-钯催化-羟基化-苯酚-吡啶酮
• “Post-It” Type Connected DNA Created with a Reversible Covalent Cross-Link
  作者：María Tomás-Gamasa、Sascha Serdjukow、Meng Su、Markus Müller、Thomas Carell

  DOI：10.1002/anie.201407854

  日期：2015.1.12

  development of a new heterobase that is held together through reversible bonding. The so‐formed cross‐link adds strong stabilization to the DNA duplex. Despite this, the cross‐link opens and closes through reversible imine bonding. Moreover, even enzymatic incorporation of the cross‐link is possible. The new principle can be used to stabilize DNA duplexes and nanostructures that otherwise require high salt

  我们报告了通过可逆键合连接在一起的新异类数据库的开发。如此形成的交联为DNA双链体增加了强大的稳定性。尽管如此，交联通过可逆的亚胺键打开和关闭。此外，甚至可以酶促地掺入交联键。新原理可用于稳定DNA双链体和纳米结构，否则它们需要高盐浓度，这可能会阻碍生物学应用。