1-[(2R,3S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-oxooxolan-2-yl]pyrimidine-2,4-dione | 179026-52-9

• 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: 1-[(2R,3S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-oxooxolan-2-yl]pyrimidine-2,4-dione
• CAS: 179026-52-9
• 化学式: C₃₆H₄₂N₂O₈Si
• 分子量: 658.824
• InChiKey: FYQOXJGTMUWLJW-KTCJXSDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.42
• 重原子数：
  47
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  1-[(2R,3S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-oxooxolan-2-yl]pyrimidine-2,4-dione 在 cerium(III) chloride 、 三氯乙酸 作用下， 以 四氢呋喃 、 乙醚 、 1,2-二氯乙烷 为溶剂， 反应 2.0h， 生成 1-[(2R,3R,4S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-4-hydroxy-5-(hydroxymethyl)-4-prop-2-enyloxolan-2-yl]pyrimidine-2,4-dione
  参考文献：
  名称：

  Stereoselective Preparation of 3'-C-Allyluridines and 3'-Spiro-gamma-Lactone Uridine Analogues.

  摘要：

  Grignard reactions of 3'-ketouridines 1a-c with allylmagnesium bromide and CeCl3 afforded novel 3'-C-allyluridines 2a-c and 3d-e. The diprotected 3'-keto nucleosides 1a-c afforded xylo-configurated compounds 2a-c and the 5'-unprotected 3'-keto nucleosides 1d-e afforded mixtures of xylo- and ribo-configurated compounds 2d/3d and 2e/3e. The allyluridine 2a was converted into the diol 4 by standard hydroboration and further oxidised to the 3'-spiro-gamma-lactone nucleoside 5. This compound and its deprotected analogue 6 are the first examples of a novel class of 3'-spiro nucleoside analogues.

  DOI：

  10.3891/acta.chem.scand.50-1030
• 作为产物：
  描述：

  5’-O-（4,4’-二甲氧基三苯甲基）-2’-O-叔丁基二甲基硅基尿苷 在 重铬酸吡啶 、 3 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以86%的产率得到1-[(2R,3S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-oxooxolan-2-yl]pyrimidine-2,4-dione
  参考文献：
  名称：

  制备2'-和3'-二氟亚甲基尿苷的3'-和2'-亚磷酰胺的新方法

  摘要：

  尿苷2a，2b，7a和7b的2'-和3'-酮衍生物与溴代二氟甲基[三（二甲基氨基）] phosph溴化物（13）和锌的一步反应，得到相应的2'-和3'-二氟亚甲基核苷图3a，3b，8a和8b具有良好的产率。除去甲硅烷基基团得到二氟亚甲基化的尿苷4a，4b，9a和9b。4a和9a的磷酸化提供了用于寡核苷酸合成的目标2'-和3'-亚磷酰胺5和10。

  DOI：

  10.1016/0040-4020(96)00364-x

文献信息

• New method for the preparation of 3′- and 2′-phosphoramidites of 2′- and 3′-difluoromethyleneuridine
  作者：Pawel J. Serafinowski、Colin L. Barnes

  DOI：10.1016/0040-4020(96)00364-x

  日期：1996.6

  step reaction of 2′- and 3′-keto derivatives of uridine 2a, 2b, 7a and 7b with bromodifluoromethyl[tris(dimethylamino)]phosphonium bromide (13) and zinc gives the corresponding 2′- and 3′-difluoromethylene nucleosides 3a, 3b, 8a and 8b in good yield. Removal of the silyl groups affords difluoromethylenated uridines 4a, 4b, 9a and 9b. Phosphitylation of 4a and 9a provides the target 2′- and 3′-phosphoramidites

  尿苷2a，2b，7a和7b的2'-和3'-酮衍生物与溴代二氟甲基[三（二甲基氨基）] phosph溴化物（13）和锌的一步反应，得到相应的2'-和3'-二氟亚甲基核苷图3a，3b，8a和8b具有良好的产率。除去甲硅烷基基团得到二氟亚甲基化的尿苷4a，4b，9a和9b。4a和9a的磷酸化提供了用于寡核苷酸合成的目标2'-和3'-亚磷酰胺5和10。
• Direct Strand Scission in Double Stranded RNA via a C5-Pyrimidine Radical
  作者：Marino J. E. Resendiz、Venkata Pottiboyina、Michael D. Sevilla、Marc M. Greenberg

  DOI：10.1021/ja300044e

  日期：2012.2.29

  Nucleobase radicals are the major family of reactive intermediates produced when nucleic acids are exposed to γ-radiolysis. The 5,6-dihydrouridin-5-yl radical (1), the formal product of hydrogen atom addition and a model for hydroxyl radical addition, was independently generated from a ketone precursor via Norrish Type I photocleavage in single and double stranded RNA. Radical 1 produces direct strand

  核碱基自由基是核酸暴露于 γ-辐射分解时产生的反应性中间体的主要家族。5,6-二氢尿苷-5-基自由基 (1) 是氢原子加成的正式产物和羟基自由基加成的模型，是通过单链和双链 RNA 中的 Norrish I 型光裂解从酮前体独立生成的。自由基 1 在 5'-相邻核苷酸处产生直接链断裂，并且在自由基产生的初始位点仅观察到少量的链断裂。链断裂优先发生在双链 RNA 中，并且在没有 O(2) 的情况下发生。断链效率的依赖性来自 5，厌氧条件下二级结构上的 6-dihydrouridin-5-yl 自由基 (1) 表明这种反应性可能有助于从羟基自由基反应中提取额外的 RNA 结构信息。改变 5'-相邻核苷酸的身份对链断裂几乎没有影响。核苷酸间链断裂通过 3'-磷酸的 β-消除发生，随后 C2'-氢原子被 1 提取。随后形成的烯烃阳离子自由基产生含有 3'-磷酸或 3'-脱氧-2'-酮核苷酸末端的 RNA
• Synthesis and NMR Spectra of Some New Carbohydrate Modified Uridine Phosphoramidites
  作者：Pawel J. Serafinowski、Colin L. Barnes

  DOI：10.1080/07328319708006222

  日期：1997.7

  The one step reaction of 2'- and 3'-keto derivatives of uridine with bromodifluoromethyl[tris(dimethylamino)]phosphonium bromide and zinc gives the corresponding 2'- and 3'-difluoromethylene nucleosides in good yield. Desilylation and phosphitylation of the resultant 2'- or 3'-hydroxyls provides the target 2'- and 3'-phosphoramidites 7 and 8 for use in oligonucleotide synthesis(1).
• Stereoselective Preparation of 3'-C-Allyluridines and 3'-Spiro-gamma-Lactone Uridine Analogues.
  作者：P. Nielsen、K. Larsen、J. Wengel、Neucírio Ricardo de Azevedo、Pedro Henrique Ferri、Kristian Rønning Pedersen、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-1030

  日期：——

  Grignard reactions of 3'-ketouridines 1a-c with allylmagnesium bromide and CeCl3 afforded novel 3'-C-allyluridines 2a-c and 3d-e. The diprotected 3'-keto nucleosides 1a-c afforded xylo-configurated compounds 2a-c and the 5'-unprotected 3'-keto nucleosides 1d-e afforded mixtures of xylo- and ribo-configurated compounds 2d/3d and 2e/3e. The allyluridine 2a was converted into the diol 4 by standard hydroboration and further oxidised to the 3'-spiro-gamma-lactone nucleoside 5. This compound and its deprotected analogue 6 are the first examples of a novel class of 3'-spiro nucleoside analogues.