triisopropylsilyl 4-pentenylideneazinate | 1181217-74-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: triisopropylsilyl 4-pentenylideneazinate
• CAS: 1181217-74-2
• 化学式: C₁₄H₂₉NO₂Si
• 分子量: 271.475
• InChiKey: HMLRGPCQEUBKLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  18.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  35.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  triisopropylsilyl 4-pentenylideneazinate 、 6-oxohexyl benzoate 在 ammonium cerium (IV) nitrate 、 5-benzyl-2-t-butyl-3-methyl-4-oxoimidazolidinium trifluoroacetate 、 水 、 碳酸氢钠 、 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 26.0h， 生成 5-(hydroxymethyl)-6-nitro-9-decenyl benzoate 、 5-(hydroxymethyl)-6-nitro-9-decenyl benzoate
  参考文献：
  名称：

  Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis

  摘要：

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

  DOI：

  10.1021/ja904504j
• 作为产物：
  描述：

  三异丙基氯硅烷 、 5-硝基-1-戊烯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 生成 triisopropylsilyl 4-pentenylideneazinate
  参考文献：
  名称：

  Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis

  摘要：

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

  DOI：

  10.1021/ja904504j