3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6-<(1R)-1-chloroacetoxyethyl>-2'-deoxyuridine | 195449-49-1

• 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: 3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6-<(1R)-1-chloroacetoxyethyl>-2'-deoxyuridine
• 英文别名: [(1R)-1-[3-[(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]-2,6-dioxopyrimidin-4-yl]ethyl] 2-chloroacetate
• CAS: 195449-49-1
• 化学式: C₂₅H₄₃ClN₂O₈Si₂
• 分子量: 591.249
• InChiKey: CEEPKLYIOLSDHB-ZVXPMLRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  38.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  118.08
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6-<(1R)-1-chloroacetoxyethyl>-2'-deoxyuridine 在 氨 、 碘 、 lead acetate 、 calcium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 环己烷 为溶剂， 反应 0.25h， 生成 3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6,1'-<(2S)-2-methyl-1-oxoethano>-α-2'-deoxyuridine
  参考文献：
  名称：

  Synthesis of Anomeric Spiro Uracil Nucleosides with an Orthoester Structure: Stereoselective Cyclization Controlled by the C6-Substituent

  摘要：

  Uracil nucleosides having an anomeric orthoester structure were synthesized fi om 2'-deoxy-6-(hydroxyalkyl)uridines through hypoiodite-initiated cyclization. The hydroxyalkyl substituent at the 6-position was found to control the anomeric stereochemistry (beta/alpha=7/1 similar to 1/46) of the cyclization. The transition state geometry of the reaction was postulated based on the X-ray crystallographic structure of the cyclized product 7 alpha to elucidate the observed stereoselectivity. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01486-x
• 作为产物：
  描述：

  3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷 在 4-二甲氨基吡啶 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 生成 3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6-<(1R)-1-chloroacetoxyethyl>-2'-deoxyuridine
  参考文献：
  名称：

  Synthesis of Anomeric Spiro Uracil Nucleosides with an Orthoester Structure: Stereoselective Cyclization Controlled by the C6-Substituent

  摘要：

  Uracil nucleosides having an anomeric orthoester structure were synthesized fi om 2'-deoxy-6-(hydroxyalkyl)uridines through hypoiodite-initiated cyclization. The hydroxyalkyl substituent at the 6-position was found to control the anomeric stereochemistry (beta/alpha=7/1 similar to 1/46) of the cyclization. The transition state geometry of the reaction was postulated based on the X-ray crystallographic structure of the cyclized product 7 alpha to elucidate the observed stereoselectivity. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01486-x

文献信息

• Face selective 6,1′-(1-oxo)ethano bridge formation of uracil nucleosides under hypoiodite reaction conditions
  作者：Atsushi Kittaka、Hajime Kato、Hiromichi Tanaka、Yumiko Nonaka、Midori Amano、Kazuo T. Nakamura、Tadashi Miyasaka

  DOI：10.1016/s0040-4020(99)00232-x

  日期：1999.4

  Synthesis of novel spiro uracil nucleosides with an anomeric orthoester structure in a stereoselective manner under the hypoio dite reaction conditions of Heusler-Kalvoda and Suárez is fully described. While 2′-deoxy-6-(hydroxymethyl)uridine 2 and 2′-deoxy-6-[(1-hydroxy-1-methyl)ethyl]uridine 4 gave β- and α-spiro nucleosides in 43–68% yields with low selectivity (), the secondary ary alcohols 3a and

  充分描述了在Heusler-Kalvoda和Suárez的低碘反应条件下以立体选择性方式合成具有异头酯原酸酯结构的新型螺尿嘧啶核苷。2'-deoxy-6-（羟甲基）尿苷2和2'-deoxy-6-[（1-羟基-1-甲基）乙基]尿苷4以43-68％的产率得到β-和α-螺代核苷，由于低选择性（），仲醇3a和3b的化学产率为68–79％，选择性明显好于（）。在该6-（羟基）尿苷同行的方向6-8，16-17，和19似乎不仅受2'-取代基的控制，而且受C6-侧链的C7-立体中心的手性的控制，就像在2'-脱氧尿苷系列中一样。该反应的过渡态的几何形状被假定基于环化产物的X射线晶体结构20 α和24 β。