(E)-6'-bromo-(5'-deoxy-5'-methylidene)-3'-O-(tert-bytuldiphenylsilyl)thymidine | 236754-84-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (E)-6'-bromo-(5'-deoxy-5'-methylidene)-3'-O-(tert-bytuldiphenylsilyl)thymidine
• 英文别名: 1-[(2R,4S,5R)-5-[(E)-2-bromoethenyl]-4-[tert-butyl(diphenyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 236754-84-0
• 化学式: C₂₇H₃₁BrN₂O₄Si
• 分子量: 555.544
• InChiKey: IPIABUQEHNBSFA-SIQNYHHWSA-N

物化性质

• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-6'-bromo-(5'-deoxy-5'-methylidene)-3'-O-(tert-bytuldiphenylsilyl)thymidine 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以95%的产率得到(E)-6'-bromo-(5'-deoxy-5'-methylidene)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：

  1-(2-deoxy-3-O-tert-butyldiphenylsilyl-β-D-erythro-pentadialdo-1,4-furanosyl)-5-methyluracil 在 亚磷酸氢二甲酯 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.33h， 生成 (E)-6'-bromo-(5'-deoxy-5'-methylidene)-3'-O-(tert-bytuldiphenylsilyl)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

文献信息

• The ‘Hirao reduction’ revisited: a procedure for the synthesis of terminal vinyl bromides by the reduction of 1,1-dibromoalkenes
  作者：Sahar Abbas、Christopher J Hayes、Stephen Worden

  DOI：10.1016/s0040-4039(00)00353-1

  日期：2000.4

  A convenient procedure for the synthesis of vinyl bromides is described, which involves the selective reduction of the corresponding 1,1-dibromoalkenes with dimethylphosphite and triethylamine. The 1,1-dibromoalkenes are obtained in excellent yields from the corresponding aldehydes via olefination with carbon tetrabromide and triphenylphosphine.

  描述了一种方便的合成乙烯基溴的方法，该方法包括用亚磷酸二甲酯和三乙胺选择性还原相应的1,1-二溴烯烃。通过与四溴化碳和三苯基膦的烯烃反应，由相应的醛以优异的收率得到1，1-二溴烯烃。
• An improved procedure for the synthesis of vinylphosphonate-linked nucleic acids
  作者：Sahar Abbas、Christopher J Hayes

  DOI：10.1016/s0040-4039(00)00653-5

  日期：2000.6

  The syntheses of a range of 5′-deoxy-5′-methylidene phosphonate-containing thymidine dimers have been achieved using a palladium-catalysed cross coupling reaction as a key step. The optimised reaction conditions comprising of palladium acetate, 1,1′-bis(diphenylphosphino)ferrocene and propylene oxide in THF were found to couple a range of H-phosphonates and vinyl bromide 3 in fair to excellent yield

  使用钯催化的交叉偶联反应作为关键步骤，已经实现了一系列含5'-脱氧-5'-亚甲基膦酸酯的胸苷二聚体的合成。发现在THF中由乙酸钯，1，1'-双（二苯基膦基）二茂铁和环氧丙烷组成的最优化反应条件公平地将一系列H-膦酸酯和乙烯基溴3偶联至优异的收率。
• A Novel Palladium-Catalysed Coupling Strategy for the Rapid Synthesis of Nucleic Acid Analogues Bearing Modified Backbones
  作者：Sahar Abbas、Christopher J. Hayes

  DOI：10.1055/s-1999-2767

  日期：1999.7