(1R,3R,4R,5S,6S,7S)-7-benzyloxy-1-benzyloxymethyl-5-methyl-6-O-phenoxythiocarbonyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane | 1179395-55-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,3R,4R,5S,6S,7S)-7-benzyloxy-1-benzyloxymethyl-5-methyl-6-O-phenoxythiocarbonyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane
• CAS: 1179395-55-1
• 化学式: C₃₄H₃₄N₂O₇S
• 分子量: 614.719
• InChiKey: BXHIPTFZUMBKSK-HELOPYHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  44.0
• 可旋转键数：
  10.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  101.01
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  (1R,3R,4R,5S,6S,7S)-7-benzyloxy-1-benzyloxymethyl-5-methyl-6-O-phenoxythiocarbonyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以10 mg的产率得到(1R,3R,4R,5R,7S)-7-benzyloxy-1-benzyloxymethyl-5-methyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane
  参考文献：
  名称：

  Synthesis and Structure of New Methylene-Bridged Hexopyranosyl Nucleoside (BHNA)

  摘要：

  A new member of hexopyranosyl nucleoside family, methylene-bridged hexopyranosyl nucleoside (BHNA), has been synthesized through generation of carbon radical at C6' in [6'S-Me, 7'S-Me]-carba-LNA T nucleoside, followed by rearrangement to C4' radical which was quenched by hydrogen atom to give BHNA. The stereoelectronic requirement for this unusual radical rearrangement has been elucidated by chemical model building and ab intio calculations to show that the coplanarity of the single electron occupied p-orbital at C6' with sigma*(O4'-C4') plays an important role for the rearrangement reaction to take place. The solution structure of BHNA has also been studied using NMR as well as by ab initio calculations. The new six-membered pyranosyl ring in BHNA, unlike other known hexopyranosyl nucleosides, adopts a twist conformation, with base moiety occupying the axial position while 3'-hydroxymethyl and 4'-hydroxyl occupying the equatorial position.

  DOI：

  10.3987/com-09-11660
• 作为产物：
  描述：

  (1R,3R,4R,5S,6S,7S)-7-benzyloxy-1-benzyloxymethyl-6-hydroxy-5-methyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane 、 硫代氯甲酸苯酯 在 吡啶 作用下， 以50%的产率得到(1R,3R,4R,5S,6S,7S)-7-benzyloxy-1-benzyloxymethyl-5-methyl-6-O-phenoxythiocarbonyl-3-(thymin-1-yl)-2-oxa-bicyclo[2.2.1]heptane
  参考文献：
  名称：

  Synthesis and Structure of New Methylene-Bridged Hexopyranosyl Nucleoside (BHNA)

  摘要：

  A new member of hexopyranosyl nucleoside family, methylene-bridged hexopyranosyl nucleoside (BHNA), has been synthesized through generation of carbon radical at C6' in [6'S-Me, 7'S-Me]-carba-LNA T nucleoside, followed by rearrangement to C4' radical which was quenched by hydrogen atom to give BHNA. The stereoelectronic requirement for this unusual radical rearrangement has been elucidated by chemical model building and ab intio calculations to show that the coplanarity of the single electron occupied p-orbital at C6' with sigma*(O4'-C4') plays an important role for the rearrangement reaction to take place. The solution structure of BHNA has also been studied using NMR as well as by ab initio calculations. The new six-membered pyranosyl ring in BHNA, unlike other known hexopyranosyl nucleosides, adopts a twist conformation, with base moiety occupying the axial position while 3'-hydroxymethyl and 4'-hydroxyl occupying the equatorial position.

  DOI：

  10.3987/com-09-11660