(Rp)-5'-O-DMT-thymidine-3'-O-(Se-methyl methanephosphonoselenolate) | 160971-73-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: (Rp)-5'-O-DMT-thymidine-3'-O-(Se-methyl methanephosphonoselenolate)
• 英文别名: 1-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[methyl(methylselanyl)phosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 160971-73-3
• 化学式: C₃₃H₃₇N₂O₈PSe
• 分子量: 699.599
• InChiKey: IEOTUSAZYWANHG-KNFAEDOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.12
• 重原子数：
  45
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (Rp)-5'-O-DMT-thymidine-3'-O-(Se-methyl methanephosphonoselenolate) 在 silver fluoride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 水 、 乙腈 为溶剂， 反应 0.41h， 生成 [(2R,3S,5R)-5-(4-benzamido-2-oxopyrimidin-1-yl)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-methylphosphoryl]oxymethyl]oxolan-3-yl] acetate
  参考文献：
  名称：

  New Approach to the Synthesis of Oligo(nucleoside methanephosphonate)s¹

  摘要：

  new method of preparation of 5'-O-DMT-(N-protected) nucleoside 3'-O-(methanephosphonofluoridates) 2 and their phosphonylating properties toward alcohols, in particular the 5'-hydroxyl groups of nucleosides (or nucleotides), is presented. Preparation of dinucleoside (3',5')-methanephosphonates 3 in solution and solid-phase synthesis of Me-Oligo 6 demonstrate the potential use of 2 as monomers.

  DOI：

  10.1021/jo951333v
• 作为产物：
  描述：

  5'-O-dimethoxytritylthymidine 3'-O-(methanephosphonoselenoanilidate) 、 碘甲烷 在 二氧化碳 、 sodium hydride 作用下， 生成 (Rp)-5'-O-DMT-thymidine-3'-O-(Se-methyl methanephosphonoselenolate) 、 (Sp)-5'-O-DMT-thymidine-3'-O-(Se-methyl methanephosphonoselenolate)
  参考文献：
  名称：

  Stereochemistry of the DBU/LiCl-Assisted Nucleophilic Substitution at Phosphorus in Nucleoside-3‘-O-(Se-methyl Methanephosphonoselenolate)s

  摘要：

  The crystal and molecular structure of diastereomerically pure N-4-benzoyl-2'-deoxycytidine 3'-O-(Se-methyl methanephosphonoselenolate (FAST-eluted) (4, R = H, B = C-Bz) and 5'-O-pixylthymidine 3'-O-(S-methyl methanephosphonothiolate (FAST-eluted) (5) have been elucidated by X-ray crystallography. The absolute configuration at the phosphorus atom in both compounds is Sp. Each FAST-4' (R = DMT, B = C-Bz) and FAST-5 (R = Px, B = Thy) in the process of DBU/LiCl-assisted condensation with 3'-O-acetyl-N-4-benzoylcytidine and 3'-O-acetylthymidine gave after deprotection (S-P)-dicytidine-(3',5')-methanephosphonate and (S-P)-dithymidine-(3',5')-methanephosphonate, respectively. Unambiguous assignment of the absolute configuration at the phosphorus in 4 (R = H, B = C-Bz) and 5 (R = Pr, B = Thy) allows for stereochemical correlation and the conclusion that DBU/LiCl-assisted nucleophilic substitution at phosphorus occurs with net inversion of configuration, in contrast to our earlier erroneous deduction,(5) Moreover, the knowledge of the absolute configuration at the phosphorus atom in both 4 (R = H, B = C-Bz) and 5 (R = Px, B = Thy) allows for assignment of the absolute configuration at phosphorus in precursors of 4' and 5, such as 5'-O-DMT-nucleoside 3'-O-methanephosphonothioanilidates (6), methanephosphonoanilidates (8), and methanephosphonoselenoanilidates (9).

  DOI：

  10.1021/jo980225g

文献信息

• New Stereospecific Method of Synthesis of [Sp]- and [Rp]-Dinucleoside-(3',5') Methanephosphonates
  作者：Lucyna A. Wozniak、Jaroslaw Pyzowski、Michal Wieczorek、Wojciech J. Stec

  DOI：10.1021/jo00099a001

  日期：1994.10

  Using a stereoretentive reaction between diastereomerically pure 5'-O-DMT-(N-protected) nucleoside 3'-O-(Se-methyl methanephosphonoselenolate)s and 3'-O-acetyl-(N-protected) nucleosides, diastereomerically pure dinucleoside-(3',5') methanephosphonates as well as ''all-Rp'' and ''all-Sp'' trimers, tetramers, and pentamers were synthesized.