3'-O-(tert-Butyldiphenylsilyl)-N³-methyl-4-thiothymidine | 163295-92-9

• 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: 3'-O-(tert-Butyldiphenylsilyl)-N³-methyl-4-thiothymidine
• CAS: 163295-92-9
• 化学式: C₂₇H₃₄N₂O₄SSi
• 分子量: 510.729
• InChiKey: JDXSOLXLYBXCTN-RBZQAINGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  35.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  65.62
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  3'-O-(tert-Butyldiphenylsilyl)-N³-methyl-4-thiothymidine 在 4-甲氧基吡啶-N-氧化物 、 5,5-二甲基-2-氯-1,3,2-二氧磷杂己内酰磷酸酯 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 4.0h， 生成 (Sp)-Thymidylyl-(3'->5')-methyl-4-thiothymidine 3'-(methylphosphonate)
  参考文献：
  名称：

  Photochemistry of Di(deoxyribonucleoside) Methylphosphonates Containing N3-Methyl-4-thiothymine

  摘要：

  (Rp)- and (Sp)-5'-N-3-methyl-4-thiothymidine 3'-(thymidinyl methylphosphonate) (Tpm(3)s(4)T) (11a and 11b), respectively, have been synthesized in order to elucidate their photochemical behavior in comparison with that of their phosphate congener 1b. The dinucleoside methylphosphonates proved to be less rapidly photolyzed than 1b and gave more photoproducts. The structure and stereochemistry of each photoproduct were determined by NMR studies. A plausible mechanism to explain the formation of the major photoproducts has been proposed. It involves two pathways: either cycloaddition or radical coupling. The former one led to thietane derivatives, the formation of which is of relevance to the mechanism to give (6-4) bipyrimidine photoproducts in DNA. Most of the other photoproducts were probably formed from a biradical generated via hydrogen abstraction from the C5 methyl of the Tp-part of each dimer. Compounds 15 which represent a new type of photoproduct in the nucleic acid series are most likely formed by this route. Another significant finding of this study was that the Rp dinucleoside methylphosphonate (11a) is a better mimic of the phosphate backbone, as found in DNA, than its Sp diastereomers (11b).

  DOI：

  10.1021/jo00103a018
• 作为产物：
  描述：

  3-甲基胸苷 在 劳森试剂 、 吡啶 、 咪唑 、 sodium methylate 、 对甲苯磺酸 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.83h， 生成 3'-O-(tert-Butyldiphenylsilyl)-N³-methyl-4-thiothymidine
  参考文献：
  名称：

  Photochemistry of Di(deoxyribonucleoside) Methylphosphonates Containing N3-Methyl-4-thiothymine

  摘要：

  (Rp)- and (Sp)-5'-N-3-methyl-4-thiothymidine 3'-(thymidinyl methylphosphonate) (Tpm(3)s(4)T) (11a and 11b), respectively, have been synthesized in order to elucidate their photochemical behavior in comparison with that of their phosphate congener 1b. The dinucleoside methylphosphonates proved to be less rapidly photolyzed than 1b and gave more photoproducts. The structure and stereochemistry of each photoproduct were determined by NMR studies. A plausible mechanism to explain the formation of the major photoproducts has been proposed. It involves two pathways: either cycloaddition or radical coupling. The former one led to thietane derivatives, the formation of which is of relevance to the mechanism to give (6-4) bipyrimidine photoproducts in DNA. Most of the other photoproducts were probably formed from a biradical generated via hydrogen abstraction from the C5 methyl of the Tp-part of each dimer. Compounds 15 which represent a new type of photoproduct in the nucleic acid series are most likely formed by this route. Another significant finding of this study was that the Rp dinucleoside methylphosphonate (11a) is a better mimic of the phosphate backbone, as found in DNA, than its Sp diastereomers (11b).

  DOI：

  10.1021/jo00103a018

文献信息

• The SP Diastereomer of a Dinucleoside Methylphosphonate Methanol Solvate Containing Thymine and N3-Methyl-4-thiothymine Bases
  作者：T. Szabó、J. Stawinski、S. Carlson、R. Norrestam

  DOI：10.1107/s0108270194006281

  日期：1995.3.15

  The structure of the non-self-complementary dinucleotide analogue (3'-deoxythymidin-3'-yl) (N-3-_ methyl-4-thio-5'-deoxythymidin-5'-yl) methylphosphonate (1) [1-(3,5-dimethyl-2-oxo-4-thio-1,2,3,4-tetrahydro-1- pyrimidinyl)-2,5-dioxoxy-beta-D-ribofuranos-5-yl (5-methyl-2,4-dioxo-1,2,3,4-tetrahydro-1- pyrimidinyl)-2,3-dideoxy-beta-D-ribofuranos-3-yl methylphosphonate], Tp(Me)msT, C22H31N4O10-PS.CH4O, has been determined and its absolute configuration at the phosphorus centre shown to be S. The 2'-deoxyribose rings of the thymidine and N-3-methyl-4-thiothymidine moieties adopt T-3(2) (C-3'-exo/C2'-endo) and T-2(3) (C2'-endo/C3'-exo) conformations, respectively. Both heterocyclic bases are oriented anti relative to the sugar rings. The deoxyribose-phosphonate backbone has an extended conformation with the bases completely unstacked and tilted away from being parallel by 16 (1)degrees.