6'-dibromo-(5'deoxy-5'-methylidene)-3'-O-(tert-butyldiphenylsilyl)thymidine | 181999-83-7

• 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: 6'-dibromo-(5'deoxy-5'-methylidene)-3'-O-(tert-butyldiphenylsilyl)thymidine
• 英文别名: 1-(2,5,6-trideoxy-6,6-dibromo-3-O-(tert-butyldiphenylsilyl)-β-D-erythro-hex-5-enofuranosyl)-5-methyluracil；1-[(2R,4S,5R)-4-[tert-butyl(diphenyl)silyl]oxy-5-(2,2-dibromoethenyl)oxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 181999-83-7
• 化学式: C₂₇H₃₀Br₂N₂O₄Si
• 分子量: 634.44
• InChiKey: DPFAIGQPIRRSIR-AOHZBQACSA-N

物化性质

• 密度：
  1.48±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.71
• 重原子数：
  36
• 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：

  6'-dibromo-(5'deoxy-5'-methylidene)-3'-O-(tert-butyldiphenylsilyl)thymidine 在 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以113 mg的产率得到6′-dibromo-(5′-deoxy-5′-methylidene)thymidine
  参考文献：
  名称：

  具有乙炔基膦酸酯键的寡核苷酸的合成和性质。

  摘要：

  乙炔基膦酸酯（EP）连接的胸苷二聚体是通过钯催化的交叉偶联反应合成的，并成功地掺入了寡核苷酸中。含有EP键的寡核苷酸可以与其互补的单链RNA（ssRNA）和单链DNA形成双链体。既包含EP键又包含2'-O，4'-C-亚甲基桥连的核酸/锁核酸的寡核苷酸对互补ssRNA表现出很强的双链体形成能力。EP修饰的寡核苷酸显示出比其天然对应物更高的核酸外切酶抗性。此外，对gapmer型反义寡核苷酸的一种EP修饰导致靶标ssRNA中切割位点的转换。所以，

  DOI：

  10.1021/acs.joc.9b01318
• 作为产物：
  描述：

  5’-O-(叔丁基二甲基甲硅烷基)胸苷 在 咪唑 、 氢氟酸 、 水 、 戴斯-马丁氧化剂 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 6'-dibromo-(5'deoxy-5'-methylidene)-3'-O-(tert-butyldiphenylsilyl)thymidine
  参考文献：
  名称：

  A Novel Palladium-Catalysed Coupling Strategy for the Rapid Synthesis of Nucleic Acid Analogues Bearing Modified Backbones

  摘要：

  DOI：

  10.1055/s-1999-2767

文献信息

• A New One-Pot Synthesis of Alkynylphosphonates
  作者：Manuel Lera、Christopher J. Hayes

  DOI：10.1021/ol0066173

  日期：2000.11.1

  A method for the palladium-catalyzed synthesis of alkynylphosphonates from 1,1-dibromo-1-alkenes has been developed. In general, the best catalyst system for this transformation was found to be Pd(OAc)(2), dppf, H-phosphonate, propylene oxide, DMF, 80 degrees C. The reaction appears tolerant of a range of functional groups in both the 1,1-dibromo-1-alkene and H-phosphonate coupling partners. The synthesis

  已经开发出一种由1，1-二溴-1-烯烃钯催化合成炔基膦酸酯的方法。通常，发现该转化的最佳催化剂体系是Pd（OAc）（2），dppf，H-膦酸酯，环氧丙烷，DMF，80°C。该反应在两个1,1-二溴-1-烯烃和H-膦酸酯偶联伙伴。骨架修饰的胸苷二聚体的合成用于说明该方法在复杂靶分子合成中的应用。
• 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。
• Replacement of the phosphodiester linkage in oligonucleotides by an acetylenic bond: Comparison between carbon-, sulfur-, and oxygen-containing analogs
  作者：Sebastian Wendeborn、Chantal Jouanno、Romain M. Wolf、Alain De Mesmaeker

  DOI：10.1016/0040-4039(96)01164-1

  日期：1996.7

  Four acetylene-containing dimers were synthesized and incorporated into oligonucleotides. The hybridization properties of the modified oligonucleotides to RNA complements and their conformational analysis are reported.

  合成了四个含乙炔的二聚体，并将其掺入寡核苷酸中。报道了修饰的寡核苷酸与RNA补体的杂交性质及其构象分析。
• Synthesis and hybridization data of oligonucleotide analogs with triazole internucleotide linkages, potential antiviral and antitumor agents
  作者：Anna Varizhuk、Alexandr Chizhov、Vladimir Florentiev

  DOI：10.1016/j.bioorg.2011.03.002

  日期：2011.6

  Triazolyl-functionalized oligonucleotide (ON) analogs have received much attention as potential antitumor and antiviral agents. The most promising of such analogs are those exhibiting high binding affinity toward native DNA/RNA, since they may prove to be efficient antisense or siRNA agents. To date, relatively few ON analogs with triazole internucleotide linkages have been described. In this paper

  三唑基官能化的寡核苷酸（ON）类似物作为潜在的抗肿瘤和抗病毒剂受到了广泛关注。此类类似物中最有前途的是那些对天然DNA / RNA表现出高结合亲和力的类似物，因为它们可能被证明是有效的反义或siRNA试剂。迄今为止，已经描述了相对较少的具有三唑核苷酸间键的ON类似物。在本文中，我们报告了改进的合成的修饰的二核苷亚磷酰胺和ON类似物与四键三唑间核苷酸键的杂交数据。我们认为，这些数据对于全面分析三唑核苷酸间键长与双链体稳定性之间的关系至关重要。
• Commercially Available 5‘-DMT Phosphoramidites as Reagents for the Synthesis of Vinylphosphonate-Linked Oligonucleic Acids
  作者：Sahar Abbas、Richard D. Bertram、Christopher J. Hayes

  DOI：10.1021/ol0166045

  日期：2001.10.1

  [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.