5'-O-[dimethyl(1,1,2-trimethylpropyl)silyl]thymidine | 123533-02-8

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 5'-O-[dimethyl(1,1,2-trimethylpropyl)silyl]thymidine
• 英文别名: 1-[(2R,4S,5R)-5-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-4-hydroxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 123533-02-8
• 化学式: C₁₈H₃₂N₂O₅Si
• 分子量: 384.548
• InChiKey: DJQUUBWRVOMPQU-RRFJBIMHSA-N

物化性质

• 熔点：
  178-180 °C
• 密度：
  1.118±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.15
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  88.1
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5'-O-[dimethyl(1,1,2-trimethylpropyl)silyl]thymidine 在 sodium azide 、 Dowex 50(H+) 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 吡啶 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 齐多夫定
  参考文献：
  名称：

  3'-取代-2'，3'-二脱氧核苷类似物的合成作为潜在的抗抑郁药

  摘要：

  3'-氨基-3'-脱氧胸苷分六个步骤制备，胸腺嘧啶核苷的总收率为67％。五个衍生品和复合他们的抗HIV活性进行了测试。

  DOI：

  10.1016/s0040-4039(00)99623-0
• 作为产物：
  描述：

  二甲基叔己基氯化硅 、 beta-胸苷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以94%的产率得到5'-O-[dimethyl(1,1,2-trimethylpropyl)silyl]thymidine
  参考文献：
  名称：

  Aza-Claisen重排：5'-支链5'-氨基胸苷的合成†

  摘要：

  '的5'-乙基取代的胸苷二聚体两者对映异构体，所述（5的合成[R - （5）'小号-构型）33A和33B分别在其中天然磷酸二酯键被酰胺基团代替（C（ 3'）-CH 2 CONH-CH（5'）（Et）），描述。它们的完全保护的衍生物35a和35b分别适合于掺入反义寡核苷酸中。出乎意料的是，尝试的Pd II催化的三氯乙酰亚氨酸7的氮杂-克莱森重排提供了非对映异构纯的环丙烷衍生物17，其结构已通过X射线分析确认。

  DOI：

  10.1002/hlca.19970800517

文献信息

• 1:1 and 1:2 complexes of Bu4NF and BF3·Et2O: Unique properties as reagents for cleavage of silyl ethers
  作者：Shun-ichi Kawahara、Takeshi Wada、Mitsuo Sekine

  DOI：10.1016/0040-4039(95)02193-0

  日期：1996.1

  A new method for removal of trialkylsilyl groups from silyl ethers using Complex A and Complex B, generated from tetrabutylammonium fluoride (TBAF) and BF3·Et2O has been developed. The desilylation by use of these boron complexes is significantly affected by the steric factor on the Si atom and the reagent.

  开发了一种新的方法，该方法使用由氟化四丁基铵（TBAF）和BF 3 ·Et 2 O生成的络合物A和络合物B从甲硅烷基醚中除去三烷基甲硅烷基。通过使用这些硼配合物的去甲硅烷基化作用显着地受到Si原子和试剂上的空间因素的影响。
• Nucleotides, Part LXV, Synthesis of 2′-Deoxyribonucleoside 5′-Phosphoramidites: New Building Blocks for the Inverse (5′-3′)-Oligonucleotide Approach
  作者：Thomas Wagner、Wolfgang Pfleiderer

  DOI：10.1002/1522-2675(20000809)83:8<2023::aid-hlca2023>3.0.co;2-p

  日期：2000.8.9

  The syntheses of the 3'-O-(4,4'-dimethoxytrityl)-protected 5'-phosphoramidites 25-28 and 5'-(hydrogen succinates) 29-32, which can be used as monomeric building blocks for the inverse (5'-3')-oligodeoxyribonucleotide synthesis are described (Scheme). These activated nucleosides and nucleotides were obtained by two slightly different four-step syntheses starting with the base-protected nucleosides 13-20. For the protection of the aglycon residues, the well-established 2-(4-nitrophenyl)ethyl (npe) and [2-(4-nitrophenyl)ethoxy]carbonyl (npeoc) groups were used. The assembly of the oligonucleotides required a slightly increased coupling time of 3 min in application of the common protocol (see Table 1). The use of pyridinium hydrochloride as an activator (instead of 1H-tetrazole) resulted in an extremely shorter activation time of 30 seconds. We established the efficiency of this inverse strategy by the synthesis of the oligonucleotide 3'-conjugates 33 and 34 which carry lipophilic caps derived from cholesterol and vitamin E, respectively, as well as by the formation of (3'-3')- and (5'-5')-internucleotide linkages (see Table 2).
• An Inverse Approach in Oligodeoxyribonucleotide Synthesis
  作者：Thomas Wagner、Wolfgang Pfleiderer

  DOI：10.1080/07328319708006249

  日期：1997.7

  We synthesized 3'-O-dimethoxytrityl-5'O-phosphoramidites and 5'-O-succinates which can be used as monomeric building blocks for the built up of oligodeoxyribonucleotides in the alternative 5'-3' direction. With this inverse strategy oligonucleotide 3'-conjugates as well as 3'-3' and 5'-5' internucleotidic linkages can be easily formed.
• MAILLARD, MICHEL;FARAJ, ABDESSLEM;FRAPPIER, FRANCOIS;FLORENT, JEAN-CLAUDE+, TETRAHEDRON LETT., 30,(1989) N5, C. 1955-1958
  作者：MAILLARD, MICHEL、FARAJ, ABDESSLEM、FRAPPIER, FRANCOIS、FLORENT, JEAN-CLAUDE+

  DOI：——

  日期：——
• Aza-Claisen Rearrangement: Synthesis of 5?-branched 5?-aminothymidines
  作者：Jochen Ammenn、Karl-Heinz Altmann、Daniel Bellu?

  DOI：10.1002/hlca.19970800517

  日期：1997.8.11

  of 5′-ethyl-substituted thymidine dimers, the (5′R)- and (5′S)-configurated 33a and 33b respectively, in which the natural phosphodiester linkage is replaced by an amide group (C(3′)-CH2CONH-CH(5′)(Et)), arc described. Their fully protected derivatives 35a and 35b, respectively, are suitable for incorporation into antisense oligonucleotides. Unexpectedly, an attempted PdII-catalysed aza-Claisen rearrangement

  '的5'-乙基取代的胸苷二聚体两者对映异构体，所述（5的合成[R - （5）'小号-构型）33A和33B分别在其中天然磷酸二酯键被酰胺基团代替（C（ 3'）-CH 2 CONH-CH（5'）（Et）），描述。它们的完全保护的衍生物35a和35b分别适合于掺入反义寡核苷酸中。出乎意料的是，尝试的Pd II催化的三氯乙酰亚氨酸7的氮杂-克莱森重排提供了非对映异构纯的环丙烷衍生物17，其结构已通过X射线分析确认。