1-[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-phenylselanyloxolan-2-yl]pyrimidine-2,4-dione | 117901-56-1

• 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: 1-[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-phenylselanyloxolan-2-yl]pyrimidine-2,4-dione
• CAS: 117901-56-1
• 化学式: C₂₇H₄₄N₂O₅SeSi₂
• 分子量: 611.788
• InChiKey: JNDJFBDBBZNEOM-MSNJVRRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-phenylselanyloxolan-2-yl]pyrimidine-2,4-dione 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Selenoxide elimination for the synthesis of unsaturated-sugar uracil nucleosides

  摘要：

  Introduction of a phenylseleno group to the sugar portion of uracil nucleosides and selenoxide elimination reactions of the resulting selenium-containing derivatives are described. A phenylselenide anion prepared by reducing (PhSe)2 with LialH4 was found to be highly reactive. By using this selenide as a nucleophile, ring openings of various types of cyclonucleosides and nucleosides having an anhydro structure in the sugar portion were accomplished. The products, which contain a phenylseleno group in the sugar portion, were oxidized with m-CPBA in CH2Cl2, and their susceptibility to the selenoxide elimination and regiochemistry of the reaction was investigated.

  DOI：

  10.1021/jo00018a038
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 lithium aluminium tetrahydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 21.17h， 生成 1-[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-phenylselanyloxolan-2-yl]pyrimidine-2,4-dione
  参考文献：
  名称：

  Selenoxide elimination for the synthesis of unsaturated-sugar uracil nucleosides

  摘要：

  Introduction of a phenylseleno group to the sugar portion of uracil nucleosides and selenoxide elimination reactions of the resulting selenium-containing derivatives are described. A phenylselenide anion prepared by reducing (PhSe)2 with LialH4 was found to be highly reactive. By using this selenide as a nucleophile, ring openings of various types of cyclonucleosides and nucleosides having an anhydro structure in the sugar portion were accomplished. The products, which contain a phenylseleno group in the sugar portion, were oxidized with m-CPBA in CH2Cl2, and their susceptibility to the selenoxide elimination and regiochemistry of the reaction was investigated.

  DOI：

  10.1021/jo00018a038

文献信息

• Synthesis of 2′-deoxy-2′-phenylselenenyl-furanosyl nucleosides from glycals using electrophilic selenium reagents. Conversion into 2′-deoxynucleosides
  作者：Yolanda Díaz、Anas El-Laghdach、Sergio Castillón

  DOI：10.1016/s0040-4020(97)00697-2

  日期：1997.8

  nucleosides have been synthesized stereoselectively from glycals using selenium reagents, and converted into 2′-deoxynucleosides by treatment with tributyltin hydride. Some of the factors which affect the stereoselectivity of the reaction are the stereochemistry at position 3, the nature of the protecting groups, the phenylselenenyl reagent and the solvent.

  已经使用硒试剂从糖中立体选择性地合成了2'-脱氧-2'-苯基硒烯基-呋喃糖基核苷，并通过氢化三丁基锡处理将其转化为2'-脱氧核苷。影响反应的立体选择性的一些因素是3位的立体化学，保护基团的性质，苯基硒烯基试剂和溶剂。
• Cleavage of Cyclic Ethers Including Oxetane and Oxolane with a Highly Nucleophilic Species of Phenylselenide Anion
  作者：Kazuhiro Haraguchi、Hiromichi Tanaka、Hiroyuki Hayakawa、Tadashi Miyasaka

  DOI：10.1246/cl.1988.931

  日期：1988.6.5

  Phenylselenide anion generated from (PhSe)2 and LiAlH4, was found to be highly reactive to various types of cyclic ethers, providing a new method to prepare γ- and δ-phenylselenenyl alcohols from oxetane and oxolane, respectively.

  发现由 (PhSe)2 和 LiAlH4 生成的苯硒阴离子对各种类型的环醚具有高度反应性，为分别从氧杂环丁烷和氧杂环戊烷制备 γ- 和 δ- 苯基硒醇提供了一种新方法。
• Radical transformations of nucleosides with (Me3Si)3SiH. Generation of a C-1’ radical through 1,2-migration of an acyloxy group
  作者：T. Gimisis、G. Ialongo、M. Zamboni、C. Chatgilialoglu

  DOI：10.1016/00404-0399(50)1340-n

  日期：1995.9

  A number of nucleoside substrates has been reduced under free radical conditions with tris(trimethylsilyl)silane. In one case a novel type of a β-(acyloxy)alkyl radical rearrangement has been observed, which leads through the generation of a C-1’ radical species to the stereoselective preparation of an α-ribonucleoside. The rate of the above 1,2-migration has been estimated, and a comparison with previously

  在自由基条件下，三（三甲基甲硅烷基）硅烷可还原许多核苷底物。在一种情况下，已经观察到新型的β-（酰氧基）烷基自由基重排，其导致C-1'自由基种类的产生导致α-核糖核苷的立体选择性制备。估计了上述1,2-迁移的速率，并与先前报告的结果进行了比较。
• HARAGUCHI, KAZUHIRO;TANAKA, HIROMICHI;HAYAKAWA, HIROYUKI;MIYASAKA, TADASH+, CHEM. LETT.,(1988) N 6, 931-934
  作者：HARAGUCHI, KAZUHIRO、TANAKA, HIROMICHI、HAYAKAWA, HIROYUKI、MIYASAKA, TADASH+

  DOI：——

  日期：——