[(2R,3S,4R,5R)-3-benzoyloxy-5-(2,4-dioxopyrimidin-1-yl)-4-iodooxolan-2-yl]methyl benzoate | 196867-33-1

• 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: [(2R,3S,4R,5R)-3-benzoyloxy-5-(2,4-dioxopyrimidin-1-yl)-4-iodooxolan-2-yl]methyl benzoate
• CAS: 196867-33-1
• 化学式: C₂₃H₁₉IN₂O₇
• 分子量: 562.318
• InChiKey: YOHZULZBRBVOAC-RSPOEFSDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4R,5R)-3-benzoyloxy-5-(2,4-dioxopyrimidin-1-yl)-4-iodooxolan-2-yl]methyl benzoate 在 二正丁基氧化锡 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以80%的产率得到[(2R,4R,5S,6S)-5-benzoyloxy-10-oxo-3,7-dioxa-1,9-diazatricyclo[6.4.0.02,6]dodeca-8,11-dien-4-yl]methyl benzoate
  参考文献：
  名称：

  2,2'-脱水核苷的制备：碱基和糖部分的区域和立体选择性修饰

  摘要：

  2'-脱氧-2'- iodonucleosides 4 - 9，从适当保护的呋喃烯糖得到的1和2具有不同的甲硅烷基化嘧啶碱，转化成相应的2,2'-脱水核苷10 - 15与C-的构型反转2'，通过在DMF中与正二丁基氧化锡一起加热。在化合物中存在的2,2'-环的C-2'区域选择性和立体有择的开口10，11，和12与叠氮化钠，得到相关2'-叠氮基-2'-脱氧核苷16，17和18分别。氢氧化钠对图12的C 12导致上述环在C-2处的区域选择性打开，同时保留了在C-2'处的构型，得到19。化合物19可以通过公认的方法直接转换为18。另一方面，化合物15可以通过在N-3–C-2'上与2,2'的开环同时存在的烯丙基溴的区域和立体选择性加成而转化为相关的2'，3'-脱水核苷23。将C-2'处的构型反转，得到中间体2'-溴-2'-脱氧核苷21，随后将其用甲醇钠处理，得到23。

  DOI：

  10.1016/s0957-4166(00)00272-x
• 作为产物：
  描述：

  3,5-di-O-benzoyl-D-xylofuranose 在 咪唑 、 N-碘代丁二酰亚胺 、 碘 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 [(2R,3S,4R,5R)-3-benzoyloxy-5-(2,4-dioxopyrimidin-1-yl)-4-iodooxolan-2-yl]methyl benzoate
  参考文献：
  名称：

  An efficient and highly stereoselective synthesis of nucleoside derivatives from furanoid 1,2-diols

  摘要：

  Reaction between suitably protected furanoid glycals 1b-4b, readily obtained from furanoid 1,2-diols (1a-4a), and different silylated pyrimidine bases, gave the corresponding 3',5'- and 3',5',6'-O-protected 2'-deoxy-2'-iodo-beta-D-xylo-pentofuranosyl 5-10 and beta-D-gluco-hexofuranosyl 11 nucleosides, respectively. Compound 5 has been transformed into its 2'-deoxy 12 and 2',3'-anhydro 14 derivatives. The high stereoselectivity of the reaction is discussed. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00332-7

文献信息

• Highly efficient synthesis of 2′,3′-didehydro-2′,3′-dideoxy-β-nucleosides through a sulfur-mediated reductive 2′,3′-trans-elimination. From iodomethylcyclopropanes to thiirane analogs
  作者：Luis Álvarez de Cienfuegos、Antonio J. Mota、Concepción Rodríguez、Rafael Robles

  DOI：10.1016/j.tetlet.2004.11.087

  日期：2005.1

  Taking into account the thiophilic properties of iodine, a very simple methodology to achieve 2,3'-didehydro-2'.3'-dideoxy-beta-nucleosides in high yield was performed, using mild, and inexpensive conditions. by means of the treatment of 2'-deoxy-3'.5'-dibenzoyl-2'-iodo-beta-nucleoside derivatives with NaHS. The process has shown to be highly dependent of the relative geometry between the iodine atom and the adjacent leaving group. In this way, different essays carried out with pyranose derivatives. have concluded in no reaction when the vicinal groups to eliminate do not adopt a trans-diaxial disposition. In addition, the treatment of 2-iodomethyl-cyclopropane-1,1-dicarboxylic acid diethyl ester under the same conditions softly and readily leads to the obtention of a mixture of the expected 2-allyl-malonic acid diethyl ester (as the minor product) and the thiirane derivative 2-thiiranytmethyl-malonic acid diethyl ester (as the major product). In this case, the responsible of the reaction progress are the nucleophilic properties of the sulfur atom rather than the thiophilic character of the iodine atom. (C) 2004 Elsevier Ltd. All rights reserved.