3,5-di-O-benzyl-1,2-O-thiocarbonyl-α-D-ribo-furanose | 581795-68-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,5-di-O-benzyl-1,2-O-thiocarbonyl-α-D-ribo-furanose
• 英文别名: (3aR,5R,6R,6aR)-6-phenylmethoxy-5-(phenylmethoxymethyl)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2-thione
• CAS: 581795-68-8
• 化学式: C₂₀H₂₀O₅S
• 分子量: 372.442
• InChiKey: QVPOYQGAUOIRIQ-NCXUSEDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  78.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,5-di-O-benzyl-1,2-O-thiocarbonyl-α-D-ribo-furanose 在 吡啶 、 氢氧化钾 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 水 、 乙腈 为溶剂， 反应 0.67h， 生成 (2R,3R,3aS,9aR)-3-Benzyloxy-2-benzyloxymethyl-7-methyl-2,3,3a,4a,5,9a-hexahydro-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6-one
  参考文献：
  名称：

  Highly β-stereoselective nucleosidation from α-d-xylo- and α-d-ribo-furanose 1,2-thiocarbonates

  摘要：

  Cyclic 1,2-thiocarbonates of alpha-D-xylo- and alpha-D-ribo-furanoses were found to be excellent glycosyl donors in mild NIS-mediated nucleophilic substitution reactions, affording beta-nucleosides with complete stereo selectivity and moderate to high yields after treatment with persilylated pyrimidinic bases. The nucleophile is believed to open the thiocarbonate ring at the anomeric position presumably via an S(N)2 mechanism. Participation of the nucleobase silylating agent [N,O-bis(trimethylsilyl)acetamide] in the mechanism of the nucleosidation step was shown, where a large excess of it has been proven to be necessary in order to achieve high yields. Absolute configurations at C-1' were ascertained by chemical correlation synthesizing the corresponding 2,2'-anhydronucleosides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.12.037
• 作为产物：
  描述：

  3,5-di-O-benzyl-D-ribofuranose 、 N,N'-硫羰基二咪唑 以 二氯甲烷 为溶剂， 反应 0.5h， 以75%的产率得到3,5-di-O-benzyl-1,2-O-thiocarbonyl-α-D-ribo-furanose
  参考文献：
  名称：

  Highly β-stereoselective nucleosidation from α-d-xylo- and α-d-ribo-furanose 1,2-thiocarbonates

  摘要：

  Cyclic 1,2-thiocarbonates of alpha-D-xylo- and alpha-D-ribo-furanoses were found to be excellent glycosyl donors in mild NIS-mediated nucleophilic substitution reactions, affording beta-nucleosides with complete stereo selectivity and moderate to high yields after treatment with persilylated pyrimidinic bases. The nucleophile is believed to open the thiocarbonate ring at the anomeric position presumably via an S(N)2 mechanism. Participation of the nucleobase silylating agent [N,O-bis(trimethylsilyl)acetamide] in the mechanism of the nucleosidation step was shown, where a large excess of it has been proven to be necessary in order to achieve high yields. Absolute configurations at C-1' were ascertained by chemical correlation synthesizing the corresponding 2,2'-anhydronucleosides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.12.037

文献信息

• Efficient and Selective Synthesis of Glycofuranosyl Azides and Nucleosides from Cyclic 1,2-Thiocarbonate Sugars
  作者：Luis Álvarez de Cienfuegos、Concepción Rodríguez、Antonio J. Mota、Rafael Robles

  DOI：10.1021/ol034975a

  日期：2003.7.1

  [reaction: see text] Cyclic 1,2-thiocarbonate sugars are convenient starting materials for the selective and efficient preparation of glycofuranosyl azides and nucleosides by regio- and stereoselective thiocarbonate ring-opening.

  [反应：见正文]环状1,2-硫代碳酸酯糖是方便的原料，用于通过区域和立体选择性硫代碳酸酯开环选择性而有效地制备糖呋喃糖基叠氮化物和核苷。
• Highly β-stereoselective nucleosidation from α-d-xylo- and α-d-ribo-furanose 1,2-thiocarbonates
  作者：Rafael Robles、Concepción Rodrı́guez、Luis Álvarez de Cienfuegos、Antonio J. Mota

  DOI：10.1016/j.tetasy.2003.12.037

  日期：2004.3

  Cyclic 1,2-thiocarbonates of alpha-D-xylo- and alpha-D-ribo-furanoses were found to be excellent glycosyl donors in mild NIS-mediated nucleophilic substitution reactions, affording beta-nucleosides with complete stereo selectivity and moderate to high yields after treatment with persilylated pyrimidinic bases. The nucleophile is believed to open the thiocarbonate ring at the anomeric position presumably via an S(N)2 mechanism. Participation of the nucleobase silylating agent [N,O-bis(trimethylsilyl)acetamide] in the mechanism of the nucleosidation step was shown, where a large excess of it has been proven to be necessary in order to achieve high yields. Absolute configurations at C-1' were ascertained by chemical correlation synthesizing the corresponding 2,2'-anhydronucleosides. (C) 2004 Elsevier Ltd. All rights reserved.