1-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-6-(2,2-dimethylpropanoyl)pyrimidine-2,4-dione | 552315-49-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-6-(2,2-dimethylpropanoyl)pyrimidine-2,4-dione
• CAS: 552315-49-8
• 化学式: C₂₆H₄₆N₂O₇Si₂
• 分子量: 554.831
• InChiKey: NUZVTLMIUUQJQV-QZNHQXDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.01
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-6-(2,2-dimethylpropanoyl)pyrimidine-2,4-dione 在 Rh/Al₂O₃ 氢气 、 triethylamine tris(hydrogen fluoride) 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 [(2R,3S,5R)-5-[(6R)-6-(2,2-dimethylpropanoyl)-2,4-dioxo-1,3-diazinan-1-yl]-3-hydroxyoxolan-2-yl]methyl benzoate
  参考文献：
  名称：

  Independent Generation and Study of 5,6-Dihydro-2‘-deoxyuridin-6-yl, a Member of the Major Family of Reactive Intermediates Formed in DNA from the Effects of γ-Radiolysis

  摘要：

  Nucleobase radicals are the major family of reactive intermediates formed when nucleic acids are exposed to gamma-radiolysis. Elucidation of their reactivity is complicated by the formation of multiple species randomly throughout the biopolymers. 5,6-Dihydro-2'-deoxyuridin-6-yl (1) was generated upon photolysis (350 nm) of the respective tert-butyl ketone (2). The radical abstracts hydrogen atoms from beta-mercaptoethanol (k = 8.8 +/- 0.5 x 10(6) M-1 s(-1)) and 2,5-dimethyltetrahydrofuran (k = 31 +/- 2.5 M-1 s(-1)). The latter was used as a model for the 2-deoxyribose component of DNA. The major product formed in the presence of O-2 was 6-hydroxy-5,6-dihydro-2'-deoxyuridine (11), which is believed to be formed directly from the peroxy precursor and not via elimination of superoxide. Small amounts of 2-deoxyribonolactone (13) were also formed under aerobic conditions. This product is believed to result from intramolecular hydrogen atom abstraction by the C6-peroxyl radical (14) and suggests that gamma-radiolysis may indirectly result in oxidation of the Cl'-position of nucleotides, despite the inaccessibility of this hydrogen in duplex DNA.

  DOI：

  10.1021/jo034038g
• 作为产物：
  描述：

  三甲基乙酰氯 、 3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷 在 仲丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 1.0h， 以30%的产率得到1-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-6-(2,2-dimethylpropanoyl)pyrimidine-2,4-dione
  参考文献：
  名称：

  Independent Generation and Study of 5,6-Dihydro-2‘-deoxyuridin-6-yl, a Member of the Major Family of Reactive Intermediates Formed in DNA from the Effects of γ-Radiolysis

  摘要：

  Nucleobase radicals are the major family of reactive intermediates formed when nucleic acids are exposed to gamma-radiolysis. Elucidation of their reactivity is complicated by the formation of multiple species randomly throughout the biopolymers. 5,6-Dihydro-2'-deoxyuridin-6-yl (1) was generated upon photolysis (350 nm) of the respective tert-butyl ketone (2). The radical abstracts hydrogen atoms from beta-mercaptoethanol (k = 8.8 +/- 0.5 x 10(6) M-1 s(-1)) and 2,5-dimethyltetrahydrofuran (k = 31 +/- 2.5 M-1 s(-1)). The latter was used as a model for the 2-deoxyribose component of DNA. The major product formed in the presence of O-2 was 6-hydroxy-5,6-dihydro-2'-deoxyuridine (11), which is believed to be formed directly from the peroxy precursor and not via elimination of superoxide. Small amounts of 2-deoxyribonolactone (13) were also formed under aerobic conditions. This product is believed to result from intramolecular hydrogen atom abstraction by the C6-peroxyl radical (14) and suggests that gamma-radiolysis may indirectly result in oxidation of the Cl'-position of nucleotides, despite the inaccessibility of this hydrogen in duplex DNA.

  DOI：

  10.1021/jo034038g

文献信息

• Independent Generation and Study of 5,6-Dihydro-2‘-deoxyuridin-6-yl, a Member of the Major Family of Reactive Intermediates Formed in DNA from the Effects of γ-Radiolysis
  作者：K. Nolan Carter、Marc M. Greenberg

  DOI：10.1021/jo034038g

  日期：2003.5.1

  Nucleobase radicals are the major family of reactive intermediates formed when nucleic acids are exposed to gamma-radiolysis. Elucidation of their reactivity is complicated by the formation of multiple species randomly throughout the biopolymers. 5,6-Dihydro-2'-deoxyuridin-6-yl (1) was generated upon photolysis (350 nm) of the respective tert-butyl ketone (2). The radical abstracts hydrogen atoms from beta-mercaptoethanol (k = 8.8 +/- 0.5 x 10(6) M-1 s(-1)) and 2,5-dimethyltetrahydrofuran (k = 31 +/- 2.5 M-1 s(-1)). The latter was used as a model for the 2-deoxyribose component of DNA. The major product formed in the presence of O-2 was 6-hydroxy-5,6-dihydro-2'-deoxyuridine (11), which is believed to be formed directly from the peroxy precursor and not via elimination of superoxide. Small amounts of 2-deoxyribonolactone (13) were also formed under aerobic conditions. This product is believed to result from intramolecular hydrogen atom abstraction by the C6-peroxyl radical (14) and suggests that gamma-radiolysis may indirectly result in oxidation of the Cl'-position of nucleotides, despite the inaccessibility of this hydrogen in duplex DNA.