5'-O-(tert-butyldimethylsilyl)-3'-O-(tert-butyldiphenylsilyl)thymidine | 166758-13-0

• 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-(tert-butyldimethylsilyl)-3'-O-(tert-butyldiphenylsilyl)thymidine
• 英文别名: TBDPS(-3)[TBDMS(-5)]2-deoxy-D-eryPenf(b)-thymin-1-yl；1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[tert-butyl(diphenyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 166758-13-0
• 化学式: C₃₂H₄₆N₂O₅Si₂
• 分子量: 594.899
• InChiKey: KEERQTKZGSYDNE-UPRLRBBYSA-N

物化性质

• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5'-O-(tert-butyldimethylsilyl)-3'-O-(tert-butyldiphenylsilyl)thymidine 在 亚磷酸氢二甲酯 、 氢氟酸 、 戴斯-马丁氧化剂 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 22.33h， 生成 (Z)-6'-bromo-(5'-deoxy-5'-methylidene)-3'-O-(tert-butyldiphenylsilyl)thymidine
  参考文献：
  名称：

  Commercially Available 5‘-DMT Phosphoramidites as Reagents for the Synthesis of Vinylphosphonate-Linked Oligonucleic Acids

  摘要：

  [GRAPHICS]Commercially available cyanoethyl phosphoramidites derived from T, d(C), d(A), and d(G) were hydrolyzed (1H-tetrazole, MeCN/H2O) to give the corresponding H-phosphonates in excellent yields. Palladium(0)-catalyzed cross-coupling of each of these with the thymidine-derived vinylbromide 2 afforded the corresponding vinylphosphonate-linked dimers T*T, d(C)*T, d(A)*T, and d(G)*T in modest to good yields. The T*T dimer was further elaborated to give a 5'-DMT-T*T-3'-CEP building block, and this was used in the automated synthesis of the TpT*TpT tetramer.

  DOI：

  10.1021/ol0166045
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 5'-O-(tert-butyldimethylsilyl)-3'-O-(tert-butyldiphenylsilyl)thymidine
  参考文献：
  名称：

  Facile Preparation of Protected Furanoid Glycals from Thymidine

  摘要：

  The synthesis of O-silyl- and O-acyl-protected furanose glycals from free thymidine was investigated. The method of glycal formation reported by Pedersen et al. was successfully expanded to include 5-ester (toluoyl) protected glycals as well as various combinations of 5'-ester and 3- and 5-tert-butyldimethylsilyl and tert-butyldiphenylsilyl protection. Gram quantities of furanoid glycals can be prepared in a few days in two-four synthetic steps in overall yields ranging from 17 to 80%.

  DOI：

  10.1021/jo970947s

文献信息

• Synthesis and some conformational features of the 5′-deoxy-5′-methylphosphonate linked dimer, 5′-deoxy-5′-C-(phosphonomethyl)thymidin-3′-yl (thymidin-5′-yl)methylphosphonate [p(ch2Tp(ch2T]
  作者：Tomas Szabó、Jacek Stawiński

  DOI：10.1016/0040-4020(95)00131-q

  日期：1995.4

  Efficient synthesis of the 5′-deoxy-5′-methylphosphonate linked thymidine dimer 11 [p(ch2Tp(ch2T] was developed via the 5′-deoxy-5′-C-(phosphonomethyl)-3′-silylated thymidine derivative 4 as a key intermediate. Conformational analysis of the sugar parts of the dimer showed that the deoxyribose residues exist in solution mainly in the S-type conformations but with a predominant contribution of antiperiplanar

  5'-脱氧-5'-甲基膦酸酯连接的胸苷二聚体11 [p（ch 2 Tp（ch 2 T]）的有效合成是通过5'-脱氧-5'-C-（膦酰基甲基）-3'-甲硅烷基化开发的胸腺嘧啶核苷衍生物4为关键中间体，对二聚体糖部分的构象分析表明，溶液中的脱氧核糖残基主要存在于S型构象中，但在两个C4'-C5'键周围的反平面旋转异构体起主要作用糖单位。
• Synthesis and properties of DNA containing a spore photoproduct analog
  作者：Eva Bürckstümmer、Thomas Carell

  DOI：10.1039/b810008j

  日期：——

  The spore photoproduct is a unique photolesion, formed in spores upon irradiation with UV light; to investigate the properties of spore photoproduct containing DNA we have synthesized 5S and 5R lesion analogs and incorporated them into DNA.

  孢子光产物是独特的光损伤，在紫外线照射下在孢子中形成；为研究含有DNA的孢子光产物的特性，我们合成了5S和5R病变类似物并将其整合到DNA中。
• <i>O</i>-(Benzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium Tetrafluoroborate (TBTU): A New Reagent for the Cleavage of Tetrahydropyranyl, Silyl and 4,4′-Dimethoxytrityl Ethers
  作者：Kanda S. Ramasamy、Devron Averett

  DOI：10.1055/s-1999-2724

  日期：1999.6

  A new reagent for the cleavage of tetrahydropyranyl, silyl and 4,4′-dimethoxytrityl ethers is described.

  描述了一种用于裂解四氢吡喃基、硅基和 4,4′-二甲氧基三苯甲基醚的新试剂。
• Efficient Desilylation of some Nucleoside Derivatives with Potassium<i>tert</i>-Butoxide in Dimethylformamide
  作者：G. Negrón、F. Vásquezy、G. Calderón、R. Cruz、R. Gaviño、G. Islas

  DOI：10.1080/00397919808004881

  日期：1998.8

  A new method for deprotecting silyl ethers of nucleosides has been established by using potassium tert-butoxide in dimethylformamide at room temperature.
• Synthesis of 5'-O-Amino-2'-Deoxypyrimidine and Purine Nucleosides: Building-Blocks for Antisense Oligonucleotides
  作者：Michel Perbost、Tomonori Hoshiko、Francois Morvan、Eric Swayze、Richard H. Griffey、Yogesh S. Sanghvi

  DOI：10.1021/jo00121a037

  日期：1995.8

  An efficient synthesis of 5'-O-amino-2'-deoxy analogs of uridine 1, thymidine 2, cytidine 3, 5-methylcytidine 3a, adenosine 4, and guanosine 5 was accomplished. The key step of 5'-O-N-bond formation in 2'-deoxynucleosides 1-5 was achieved via a Mitsunobu reaction in excellent yields. The 5'-O-amino nucleosides 1-5 are useful building-blocks for the synthesis of nucleoside dimers linked by a methylene(methylimino) (MMI) bridge. MMI is a novel phosphate surrogate for antisense oligonucleosides.