[(3aR,5R,6S,6aR)-6-(cyanomethyl)-2,2-dimethyl-5-[(propan-2-ylamino)methyl]-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl] [(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl [(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] phosphite | 320784-45-0

• 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: [(3aR,5R,6S,6aR)-6-(cyanomethyl)-2,2-dimethyl-5-[(propan-2-ylamino)methyl]-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl] [(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl [(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] phosphite
• CAS: 320784-45-0
• 化学式: C₄₅H₇₅N₆O₁₄PSi₂
• 分子量: 1011.27
• InChiKey: LNPWRULSVXHCTA-QUVMGMQGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  68
• 可旋转键数：
  20
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  227
• 氢给体数：
  3
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  [(3aR,5R,6S,6aR)-6-(cyanomethyl)-2,2-dimethyl-5-[(propan-2-ylamino)methyl]-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl] [(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl [(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] phosphite 在 苯基二硫化物 作用下， 以61%的产率得到2-[(3aR,5R,6S,6aR)-6-[[(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinothioyl]oxy-2,2-dimethyl-5-[(propan-2-ylamino)methyl]-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl]acetonitrile
  参考文献：
  名称：

  Study on the diastereoselective synthesis of dithymidine phosphorothioates through a d-xylose derived chiral auxiliary and development of a novel catalyst

  摘要：

  1,2-Di-O-isopropylidene-3-C-cyanoethyl-5-deoxy-5-isopropylamino-D-xylofuranose 16a was synthesized The use of 16a as a chiral auxiliary led to the diastereoselective formation of dithymidine phosphorothioate. The chiral auxiliary was easily removed by treatment with concentrated ammonia. 2-Mesityl-4,5-dicyanoimidazole displays higher diastereoselectivity than the 2-bromo-4,5-dicyanoimidazole in the coupling reaction. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01678-6
• 作为产物：
  描述：

  1,2-O-isopropylidene-5-O-(tert-butyl)dimethylsilyl-α-D-xylofuranoside 在 吡啶 、 chromium(VI) oxide 、 叔丁基过氧化氢 、 锂硼氢 、 草酰氯 、 四丁基氟化铵 、 乙酸酐 、 苄基三甲基氢氧化铵 、 三乙酰氧基硼氢化钠 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 2-溴-4,5-二氰基咪唑 、 三氯化磷 作用下， 以 四氢呋喃 、 氘代氯仿 、 二氯甲烷 、 二乙二醇二甲醚 、 1,2-二氯乙烷 为溶剂， 生成 [(3aR,5R,6S,6aR)-6-(cyanomethyl)-2,2-dimethyl-5-[(propan-2-ylamino)methyl]-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-yl] [(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl [(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] phosphite
  参考文献：
  名称：

  Study on the diastereoselective synthesis of dithymidine phosphorothioates through a d-xylose derived chiral auxiliary and development of a novel catalyst

  摘要：

  1,2-Di-O-isopropylidene-3-C-cyanoethyl-5-deoxy-5-isopropylamino-D-xylofuranose 16a was synthesized The use of 16a as a chiral auxiliary led to the diastereoselective formation of dithymidine phosphorothioate. The chiral auxiliary was easily removed by treatment with concentrated ammonia. 2-Mesityl-4,5-dicyanoimidazole displays higher diastereoselectivity than the 2-bromo-4,5-dicyanoimidazole in the coupling reaction. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01678-6

文献信息

• Stereoselective synthesis of dithymidine phosphorothioates using d -xylose derived chiral auxiliaries
  作者：Yixin Lu、George Just

  DOI：10.1016/s0040-4020(00)01170-4

  日期：2001.2

  Different sized catalysts 1, 2, 5 and 7 were prepared and used as the activators in the coupling reactions of phosphoramidites with nucleosides. d-Xylose derived chiral auxiliary 22a has been synthesized and applied for the stereoselective synthesis of dithymidine phosphorothioates 27. The mechanisms of the coupling reactions are discussed.

  不同尺寸的催化剂1，2，5和7制备并用作与核苷亚磷酰胺的偶联反应的活化剂。d-木糖衍生的手性助剂22a已合成，并用于二硫代磷酸硫代胸苷27的立体选择性合成。讨论了偶联反应的机理。