(2'-R)-[2'-2H]-2'-deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-β-D-uridine | 156726-71-5

• 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'-R)-[2'-2H]-2'-deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-β-D-uridine
• 英文别名: 1-[(6aR,8R,9R,9aS)-9-deuterio-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]pyrimidine-2,4-dione
• CAS: 156726-71-5
• 化学式: C₂₁H₃₈N₂O₆Si₂
• 分子量: 471.706
• InChiKey: PEDMJTBGYAMVDO-IWKMDEJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2'-R)-[2'-2H]-2'-deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-β-D-uridine 在 吡啶 、 氟化铵 、 ammonium hydroxide 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 乙腈 为溶剂， 生成 (2'R)-N⁴-benzoyl-2'-deoxy[2'-2H]cytidine
  参考文献：
  名称：

  Sonochemical and Triethylborane-Induced Tin Deuteride Reduction for the Highly Diastereoselective Synthesis of (2'R)-2'-Deoxy[2'-2H]ribonucleoside Derivatives

  摘要：

  For the NMR spectroscopic conformational analysis of a sugar moiety in a DNA complex with a protein or a drug, (2'R)- and/or (2'S)-2'-deoxy[2'-H-2]ribonucleoside derivatives with high purity are useful. To develop a highly diastereoselective and efficient method for the synthesis of(2'R)-2'-deoxy[2'-H-2]ribonucleoside derivatives, studies of leaving groups (OPTC, Br) at the 2' position of nucleosides, of the effects of reaction temperature on diastereoselectivity, of radical generation (ultrasound irradiation, Et(3)B) at temperatures as low as -70 degrees C, and of protecting groups for the 3' and 5' hydroxyl groups (benzoate, TPDS) of nucleosides were carried out. Bu(3)Sn(2)H-reductive deuteration of 3',5'-di-0-benzoyl-2'-bromo-2'-deoxyuridine under high-intensity ultrasound irradiation at -71 degrees C induced notably efficient deuterium incorporation to afford a highly diastereoselective 3',5'-di-0-benzoyl-2'-deoxy[2'-H-2]uridin [(2'R):(2'S) = 96:4]. The use of Et(3)B, as an alternative radical generator, toward 2'-bromo-2'-deoxy-3',5'-0-TPDS-ribonucleosides at <--70 degrees C made it feasible to perform the reaction on a preparative scale, and provided excellent diastereoselectivity (2'-deoxyadenosine, thymidine, and 2'-deoxyuridine derivatives >99:1 which were converted to (2'R)-2'-deoxy[2'-H-2]cytidine derivatives, guanosine derivative = 91:9).

  DOI：

  10.1021/jo00126a058
• 作为产物：
  描述：

  3',5'-O-(1,1,3,3-四异丙基-1,3-二硅氧烷)尿苷 在 偶氮二异丁腈 、 sodium hydride 、 氘代三正丁基锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 4.0h， 生成 (2'-R)-[2'-2H]-2'-deoxy-3',5'-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-β-D-uridine
  参考文献：
  名称：

  通过硫代氨基甲酸酯衍生物对脂族醇进行基于自由基的脱氧

  摘要：

  在NaH存在下，将醇与异硫氰酸苯酯反应制得的N-苯基硫代氨基甲酸酯，在自由基条件下，用各种硅烷（如三乙基硅烷，三苯基硅烷和三（三甲基甲硅烷基）硅烷）和三丁基锡烷还原，得到苯甲酸酯的脱氧产物。相应的醇，收率很高。该反应不仅适用于简单的脂族醇，而且适用于糖和核苷。在相似条件下，还研究了使用氘代硅烷和氘代锡烷烷的区域选择性和立体选择性氘代。

  DOI：

  10.1016/s0040-4020(01)81751-8

文献信息

• Selective site deuteration on the sugar ring as an efficient marker of conformation in nucleosides: The CD stretching mode of the (2′-R)-[2′-2H]-2′-deoxyuridine and its 3′,5′-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-derivative
  作者：L. Grajcar、M.H. Baron、S. Becouarn、S. Czernecki、J.M. Valery、C. Reiss

  DOI：10.1016/0584-8539(94)80022-7

  日期：1994.6

  A uridine specifically deuterated on the deoxyribose ring at the C2', and the same compound in a more rigid form, due to a chemically fused ring (between C3' and C5'), have been synthesized. By NMR, the coupling constants J1'-2' and J3'-4' have been determined and the populations of the C2'-endo and C3'-endo conformers have been deduced for the two compounds. Comparison of these results with an FTIR and Raman study of the stretching mode nuC-D on the C2' site allows a specific assignment of each observed band to one of the two classes of conformers. This enables us to consider the further step: the direct recognition, by IR and Raman spectroscopies, of the local conformation at a specific site of a synthetic oligonucleotide, using the nuCD signals as marker bands.
• Tris(trimethylsilyl)[2H]silane-triethylborane system producing the highly diastereoselective deuteration (&gt; 99:1) of 2′-bromo-2′-deoxy- and 2′-O-phenoxythiocarbonylribonucleosides at 0°C
  作者：Etsuko Kawashima、Seishiro Uchida、Masayoshi Miyahara、Yoshiharu Ishido

  DOI：10.1016/s0040-4039(97)01722-x

  日期：1997.10

  Reductive protylation and deuteration reactions using (Me3Si)(3)SiH- and (Me3Si)(3)(SiH)-H-2-Et3B systems were investigated in view of the differences in bond energy and bond length between the Si-H of (Me3Si)(3)SiH and the Sn-H of Bu3SnH. Higher diastereoselectivity was obtained in comparison with the reactions using the Bu3SnH - and (Bu3SnH)-H-2-Et3B systems; the (Me3Si)(3)SiH system gave remarkable diastereoselectivity of 98.7% at 0 degrees C, whereas the other system required temperatures below -70 degrees C. (C) 1997 Elsevier Science Ltd.
• Radical-based deoxygenation of aliphatic alcohols via thioxocarbamate derivatives
  作者：Makoto Oba、Kozaburo Nishiyama

  DOI：10.1016/s0040-4020(01)81751-8

  日期：1994.8

  N-Phenylthioxocarbamates, obtained from the reaction of alcohols with phenyl isothiocyanate in the presence of NaH, were reduced with various silanes such as triethylsilane, triphenylsilane, and tris(trimethylsilyl)silane, as well as tributylstannane under radical conditions to give deoxygenated products of the corresponding alcohols in excellent yields. The reaction was applicable to not only simple aliphatic

  在NaH存在下，将醇与异硫氰酸苯酯反应制得的N-苯基硫代氨基甲酸酯，在自由基条件下，用各种硅烷（如三乙基硅烷，三苯基硅烷和三（三甲基甲硅烷基）硅烷）和三丁基锡烷还原，得到苯甲酸酯的脱氧产物。相应的醇，收率很高。该反应不仅适用于简单的脂族醇，而且适用于糖和核苷。在相似条件下，还研究了使用氘代硅烷和氘代锡烷烷的区域选择性和立体选择性氘代。
• Sonochemical and Triethylborane-Induced Tin Deuteride Reduction for the Highly Diastereoselective Synthesis of (2'R)-2'-Deoxy[2'-2H]ribonucleoside Derivatives
  作者：Etsuko Kawashima、Yukio Aoyama、Takeshi Sekine、Masayoshi Miyahara、Mohamed F. Radwan、Eiichi Nakamura、Masatsune Kainosho、Yoshimasa Kyogoku、Yoshiharu Ishido

  DOI：10.1021/jo00126a058

  日期：1995.10

  For the NMR spectroscopic conformational analysis of a sugar moiety in a DNA complex with a protein or a drug, (2'R)- and/or (2'S)-2'-deoxy[2'-H-2]ribonucleoside derivatives with high purity are useful. To develop a highly diastereoselective and efficient method for the synthesis of(2'R)-2'-deoxy[2'-H-2]ribonucleoside derivatives, studies of leaving groups (OPTC, Br) at the 2' position of nucleosides, of the effects of reaction temperature on diastereoselectivity, of radical generation (ultrasound irradiation, Et(3)B) at temperatures as low as -70 degrees C, and of protecting groups for the 3' and 5' hydroxyl groups (benzoate, TPDS) of nucleosides were carried out. Bu(3)Sn(2)H-reductive deuteration of 3',5'-di-0-benzoyl-2'-bromo-2'-deoxyuridine under high-intensity ultrasound irradiation at -71 degrees C induced notably efficient deuterium incorporation to afford a highly diastereoselective 3',5'-di-0-benzoyl-2'-deoxy[2'-H-2]uridin [(2'R):(2'S) = 96:4]. The use of Et(3)B, as an alternative radical generator, toward 2'-bromo-2'-deoxy-3',5'-0-TPDS-ribonucleosides at <--70 degrees C made it feasible to perform the reaction on a preparative scale, and provided excellent diastereoselectivity (2'-deoxyadenosine, thymidine, and 2'-deoxyuridine derivatives >99:1 which were converted to (2'R)-2'-deoxy[2'-H-2]cytidine derivatives, guanosine derivative = 91:9).