1-O-acetyl-5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-2-phenylthio-D-erythro-pentofuranose | 132436-48-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-O-acetyl-5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-2-phenylthio-D-erythro-pentofuranose
• 英文别名: [(3R,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-phenylsulfanyloxolan-2-yl] acetate
• CAS: 132436-48-7
• 化学式: C₂₉H₃₄O₄SSi
• 分子量: 506.738
• InChiKey: UOUWTXJRUHBTRA-QFIHXRDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  35.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1-O-acetyl-5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-2-phenylthio-D-erythro-pentofuranose 在 四氯化锡 三正丁胺 、 四丁基氟化铵 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 xylene 为溶剂， 反应 9.5h， 生成 N⁴-acetyl-2',3'-didehydro-2',3'-dideoxycytidine
  参考文献：
  名称：

  Stereoselectivity in the Coupling Reaction between 2-Phenylthio-2,3-dideoxyribose and Silylated Pyrimidine Bases

  摘要：

  在SnCl4存在下，2-α-苯硫基-2,3-双脱氧核糖与硅化嘧啶碱基的耦合反应以立体选择性方式进行，得到β-异构体。这些核苷随后通过氧化后进行热消除，转化为2′,3′-双脱氧-2′,3′-双脱氢核苷。

  DOI：

  10.1246/cl.1990.1459
• 作为产物：
  描述：

  (3R,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-phenylsulfanyloxolan-2-one 在 吡啶 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 1-O-acetyl-5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-2-phenylthio-D-erythro-pentofuranose
  参考文献：
  名称：

  控制2'-脱氧核糖核苷合成中糖基化立体化学的一般方法

  摘要：

  2-芳基亚磺酰基-O-乙酰基核糖苷6与甲硅烷基化的胸腺嘧啶11的糖基化反应产生具有高β-选择性的2'-脱氧核糖核苷。描述了这种指导作用在抗逆转录病毒药D4T，2的合成中的应用。

  DOI：

  10.1016/s0040-4039(00)98793-8

文献信息

• Nitrogen Glycosylation Reactions Involving Pyrimidine and Purine Nucleoside Bases with Furanoside Sugars
  作者：Lawrence J. Wilson、Michael W. Hager、Yahya A. El-Kattan、Dennis C. Liotta

  DOI：10.1055/s-1995-4142

  日期：1995.12

  Different approaches for the synthesis of nucleoside analogs (potential HIV inhibitors) are described. Starting from a suitably substituted furanose ring, it is demonstrated that a high facial stereocontrol of the glycosylation reaction can be effected. Different reaction conditions including Lewis acid promoted, SN2 displacement and some enzymatic methodologies for the stereoselective synthesis of these compounds are reviewed.

  本文介绍了合成核苷类似物（潜在的HIV抑制剂）的不同方法。从合适的取代呋喃糖环开始，证明了可以实现高面部立体控制的糖基化反应。综述了包括路易斯酸促进、SN2取代以及一些酶学方法在内的不同反应条件，用于这些化合物的立体选择性合成。
• Synthesis and in Vitro Evaluation of 5-<i>closo</i>- and 5-<i>nido</i>-Orthocarboranyluridines as Boron Carriers
  作者：Ken-ichiro Imamura、Yoshinori Yamamoto

  DOI：10.1246/bcsj.70.3103

  日期：1997.12

  Sugar-part modified closo-carboranyluridines, 5-(o-carboran-1-yl)-2′,3′-dideoxy-3′-thiauridine 5 and 5-(o-carboran-1-yl)-2′,3′-dideoxy-2′α-phenylthiouridine 6, were synthesized. These newly synthesized closo-carboranyluridines, 5 and 6, and previously synthesized 5-(o-carboran-1-yl)uridine 1 were converted to the corresponding nido-carboranyluridines 18, 19, and 17, respectively. Water-solubility of nido-type 17 was about 100 times higher than that of its closo-counterpart 1. Water-solubilities of sugar modified nido-types 18 and 19 were about 1000 times higher than those of their closo-counterparts 5 and 6 . Cytotoxicities of the nido-types (17 and 19) were about 10 times lower than those of the corresponding closo-counterparts (1 and 6, respectively). Cellular uptake of the nido-types (17 and 19) was in the level similar to that of the closo-counterparts (1 and 6, respectively), although it is often believed that cellular uptake of hydrophilic carboranes (nido-forms) is much lower than that of lipophilic closo-carboranes.

  合成了经糖部分修饰的闭硼酰尿苷，即 5-(邻碳硼烷-1-基)-2′,3′-二脱氧-3′-噻尿苷 5 和 5-(邻碳硼烷-1-基)-2′,3′-二脱氧-2′α-苯硫依啶 6。这些新合成的闭硼酰尿苷 5 和 6 以及之前合成的 5-(邻硼烷基)尿苷 1 分别被转化成相应的尼多硼酰尿苷 18、19 和 17。尼多型 17 的水溶性比其闭合型 1 高出约 100 倍。糖修饰的尼多类 18 和 19 的水溶性是其闭合对应物 5 和 6 的约 1000 倍。尼多类（17 和 19）的细胞毒性比相应的闭合对应物（1 和 6）低约 10 倍。尽管人们通常认为亲水性碳硼烷（nido-forms）的细胞吸收率远远低于亲脂性碳硼烷（closeno-carboranes），但nido-type（17 和 19）的细胞吸收率与closeno-counterparts（分别为 1 和 6）的细胞吸收率相近。
• Synthesis and in vitro evaluation of sugar-modified carboranyluridines
  作者：Ken-ichiro Imamura、Yoshinori Yamamoto

  DOI：10.1016/0960-894x(96)00330-7

  日期：1996.8

  Sugar-part modified carboranyluridines 5 and 6 were synthesized. Although cytotoxicities of 5 and 6 were similar to those of 1 and 2 having ordinary sugar parts, selective uptake of 6 into TIG-1-20 cells was accomplished by changing the sugar part to a sulfur containing one. Copyright (C) 1996 Elsevier Science Ltd
• Synthesis of 2',3'-Didehydro-2',3'-dideoxynucleosides Utilizing Coupling Reactions between Nucleic Bases and Phenylthio-substituted 2,3-Dideoxyribose
  作者：Hiroshi Kawakami、Takashi Ebata、Koshi Koseki、Katsuya Matsumoto、Hajime Matsushita、Yoshitake Naoi、Kazuo Ito

  DOI：10.3987/com-91-5884

  日期：——

  Stereoselectivities in coupling reactions between silylated pyrimidine bases and 3- or 2-alpha-phenylthio-2,3-dideoxyribose were examined. In the former case, no stereoselectivies were observed when the coupling reactions were performed either with 1-chlorosugar in an S(N)2 mode or in the presence of Lewis acids as catalyst in an S(N)1 mode. Coupling reaction with 2-alpha-phenylthio-2,3-dideoxyribose in the presence of Lewis acids, especially SnCl4, proceeded with good stereoselectivity to give anomeric mixtures of alpha:beta = 1:9. All these nucleosides were converted to 2',3'-didehydro-2',3'-dideoxynucleosides by oxidation to sulfoxides followed by thermal elimination of sulfenic acid.
• WILSON, LAWRENCE J.;LIOTTA, DENNIS, TETRAHEDRON LETT., 31,(1990) N3, C. 1815-1818
  作者：WILSON, LAWRENCE J.、LIOTTA, DENNIS

  DOI：——

  日期：——