ethyl (E,E)-6-aza-10-bromo-6-(p-toluenesulfonyl)-9-[(triethyl)silyl]deca-2,8-dienoate | 1254356-31-4

• 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: ethyl (E,E)-6-aza-10-bromo-6-(p-toluenesulfonyl)-9-[(triethyl)silyl]deca-2,8-dienoate
• 英文别名: ethyl (E)-5-[[(E)-4-bromo-3-triethylsilylbut-2-enyl]-(4-methylphenyl)sulfonylamino]pent-2-enoate
• CAS: 1254356-31-4
• 化学式: C₂₄H₃₈BrNO₄SSi
• 分子量: 544.626
• InChiKey: CTHWNBXCRHBDRR-XYKIQLICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (E,E)-6-aza-10-bromo-6-(p-toluenesulfonyl)-9-[(triethyl)silyl]deca-2,8-dienoate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (4aS*,5R*,7R*,7aR*)-5-ethoxycarbonyl-1-(p-toluenesulfonyl)-7-[(triethyl)silyl]octahydro-1H-[2]pyrindene 、 (4aR*,5S*,7S*,7aR*)-5-ethoxycarbonyl-1-(p-toluenesulfonyl)-7-[(triethyl)silyl]octahydro-1H-[2]pyrindene 、 (4RS,5RS)-4-(ethoxycarbonylmethyl)-1-(p-toluenesulfonyl)-5-[1-{(triethyl)silyl}vinyl]piperidine
  参考文献：
  名称：

  Stereoselective Synthesis of 2,4,5-Trisubstituted Piperidines via Radical Cyclization

  摘要：

  A novel approach to 2,4,5-trisubstituted piperidines is reported, involving the 6-exo cyclization of stabilized radicals onto alpha,beta-unsaturated esters. Only two of the four possible diastereoisomers are observed, with diastereomeric ratios ranging from 3:2 to 40:1 when the radical stabilizing group is vinyl or phenyl. Cyclization of a (triethylsilyl)vinyl-stabilized radical gives the corresponding piperidine radical as a single diastereoisomer that may either be trapped by tributyltin hydride to afford the 2,4,5-trisubstituted piperidine or undergo a second 5-endo cyclization onto the (triethylsilyl)vinyl substituent to produce the 3,5,7-trisubstituted octahydro[2]pyrindene as a single diastereoisomer.

  DOI：

  10.1021/jo101631y
• 作为产物：
  描述：

  (E)-4-acetoxy-3-(triethylsilyl)but-2-en-1-ol 在 四氯化碳 、 四溴化碳 、 caesium carbonate 、 胍 、 三苯基膦 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 40.83h， 生成 ethyl (E,E)-6-aza-10-bromo-6-(p-toluenesulfonyl)-9-[(triethyl)silyl]deca-2,8-dienoate
  参考文献：
  名称：

  Stereoselective Synthesis of 2,4,5-Trisubstituted Piperidines via Radical Cyclization

  摘要：

  A novel approach to 2,4,5-trisubstituted piperidines is reported, involving the 6-exo cyclization of stabilized radicals onto alpha,beta-unsaturated esters. Only two of the four possible diastereoisomers are observed, with diastereomeric ratios ranging from 3:2 to 40:1 when the radical stabilizing group is vinyl or phenyl. Cyclization of a (triethylsilyl)vinyl-stabilized radical gives the corresponding piperidine radical as a single diastereoisomer that may either be trapped by tributyltin hydride to afford the 2,4,5-trisubstituted piperidine or undergo a second 5-endo cyclization onto the (triethylsilyl)vinyl substituent to produce the 3,5,7-trisubstituted octahydro[2]pyrindene as a single diastereoisomer.

  DOI：

  10.1021/jo101631y