2,2'-Anhydro-1-<3',5'-bis-O-(tert-butyldimethylsilyl)-β-D-arabinofuranosyl>thymine | 127941-51-9

• 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: 2,2'-Anhydro-1-<3',5'-bis-O-(tert-butyldimethylsilyl)-β-D-arabinofuranosyl>thymine
• 英文别名: 3',5'-di-O-t-butyldimethylsilyl-O²,2'-cyclothymidine；(2R,4R,5R,6S)-5-[tert-butyl(dimethyl)silyl]oxy-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-11-methyl-3,7-dioxa-1,9-diazatricyclo[6.4.0.02,6]dodeca-8,11-dien-10-one
• CAS: 127941-51-9
• 化学式: C₂₂H₄₀N₂O₅Si₂
• 分子量: 468.741
• InChiKey: PMFFKXCOYPLOJF-VXIBKDFQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  69.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,2'-Anhydro-1-<3',5'-bis-O-(tert-butyldimethylsilyl)-β-D-arabinofuranosyl>thymine 在 N-溴代丁二酰亚胺(NBS) 、 potassium tert-butylate 、 四氯化锡 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 1-(2-bromo-1-C-cyano-2-deoxy-β-D-arabino-pentofuranosyl)thymine
  参考文献：
  名称：

  Synthesis and Biological Evaluation of 1′-C-Cyano-Pyrimidine Nucleosides

  摘要：

  2'-Deoxy-, 2'-bromo-, and arabine-1'-C-cyano-pyrimidine nucleosides were synthesized from O-2,2'-cyclouridine. Incorporation of cyano group at the anomeric position was achieved by treatment of 1',2'-unsaturated uridine with NBS in the presence of pivalic acid followed by TMS-cyanide and stannic chloride. Antineoplastic and antiviral activities of those compounds are also discussed.

  DOI：

  10.1080/07328319608002386
• 作为产物：
  描述：

  (2R,3R,3aS,9aR)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-7-methyl-2,3,3a,7,8,9a-hexahydro-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6-one 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以70%的产率得到2,2'-Anhydro-1-<3',5'-bis-O-(tert-butyldimethylsilyl)-β-D-arabinofuranosyl>thymine
  参考文献：
  名称：

  Unprecedented chlorination of 2,2′-anhydro-5,6-dihydropyrimidine nucleosides during DDQ oxidation

  摘要：

  Chloride ion, derived from 2,3-dichloro-5,6-dicyanohydroquinone (DDHQ), was found to participate in opening of the 2,2'-anhydro bond of 5,6-dihydropyrimidine nucleosides, but not their 5,6-unsaturated counterparts. The increased basicity of the nucleosidic nitrogen is believed to be a factor in this unprecedented reaction. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00727-2

文献信息

• Diastereomeric 5,6-Dihydrothymidines. Preparation, Stereochemical Assignments, and MnO2 Oxidation Studies of Thymidines
  作者：Palle V. P. Pragnacharyulu、Chandra Vargeese、Michael Mc Gregor、Elie Abushanab

  DOI：10.1021/jo00115a026

  日期：1995.5

  A useful method for the stereospecific synthesis of beta-thymidine and beta-5,6-dihydrothymidine nucleosides is described. Condensation of methyl 2-formylpropionate and methyl methacrylate with oxazolines 8 furnished the corresponding 2,2'-anhydrothymidine 11 and a 2:1 diastereomeric mixture of 2,2'-anhydro-5,6-dihydrothymidine 10, respectively. While DDQ oxidation of 10 furnished 11, active MnO2 resulted in a selective dehydrogenation hitherto unreported in nucleoside chemistry. The minor diasteromer 10b was quantitatively converted to 11, leaving 10a unchanged. A plausible explanation for this selectivity was based on the stereochemistry at C5 which was determined by one-dimensional NOE studies.
• Synthesis and Biological Evaluation of 1′-<i>C</i>-Cyano-Pyrimidine Nucleosides
  作者：Yuichi Yoshimura、Fumitaka Kano、Shuichi Miyazaki、Noriyuki Ashida、Shinji Sakata、Kazuhiro Haraguchi、Yoshiharu Itoh、Hiromichi Tanaka、Tadashi Miyasaka

  DOI：10.1080/07328319608002386

  日期：1996.1

  2'-Deoxy-, 2'-bromo-, and arabine-1'-C-cyano-pyrimidine nucleosides were synthesized from O-2,2'-cyclouridine. Incorporation of cyano group at the anomeric position was achieved by treatment of 1',2'-unsaturated uridine with NBS in the presence of pivalic acid followed by TMS-cyanide and stannic chloride. Antineoplastic and antiviral activities of those compounds are also discussed.
• Unprecedented chlorination of 2,2′-anhydro-5,6-dihydropyrimidine nucleosides during DDQ oxidation
  作者：Palle V.P. Pragnacharyulu、Elie Abushanab

  DOI：10.1016/s0040-4039(97)00727-2

  日期：1997.5

  Chloride ion, derived from 2,3-dichloro-5,6-dicyanohydroquinone (DDHQ), was found to participate in opening of the 2,2'-anhydro bond of 5,6-dihydropyrimidine nucleosides, but not their 5,6-unsaturated counterparts. The increased basicity of the nucleosidic nitrogen is believed to be a factor in this unprecedented reaction. (C) 1997 Elsevier Science Ltd.