N,N-Bis(trimethylsilyl)-2-carbethoxy-2-propen-1-amine

• 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: N,N-Bis(trimethylsilyl)-2-carbethoxy-2-propen-1-amine
• 英文别名: Ethyl 2-[[bis(trimethylsilyl)amino]methyl]prop-2-enoate
• 化学式: C₁₂H₂₇NO₂Si₂
• 分子量: 273.523
• InChiKey: UDJDAVBNDQFUNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.08
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(氯甲基)丙烯酸乙酯 、 lithium hexamethyldisilazane 在 silver(I) iodide 作用下， 生成 N,N-Bis(trimethylsilyl)-2-carbethoxy-2-propen-1-amine
  参考文献：
  名称：

  Silver iodide mediated amination reaction of allylic chlorides with lithium bis(trimethylsilyl)amide: a new synthetic method of N,N-disilylallylamines via lithium amide argentates

  摘要：

  The nucleophilic substitution reaction of allylic chlorides with lithium bis(trimethylsilyl)amide (1) in the presence of silver halides has been studied in detail. Silver iodide (AgI) was found to be most effective for facilitation of the amination reaction. The reaction of alkyl-substituted allylic chlorides proceeded smoothly in S(N)2 fashion to give N,N-disilylallylamines in high yields when 0.1 or 0.5 equiv of AgI was used as an additive, whereas a stoichiometric amount of AgI was indispensable in the reaction of allylic chlorides having a phenyl group. The reaction of geranyl or neryl chloride proceeded with retention of configuration of the C=C bond to give only one isomer 4 or 5, respectively. The oxygen-containing functional groups and chlorine remained intact during the reaction. The reaction of alpha-silylmetallyl chloride 17 proceeded in an S(N)2' manner to afford (Z)-allylamine 18. So as to disclose the active species in the AgI-mediated reaction, the variable low-temperature C-13 NMR experiments using the mixture of AgI and 1 in THF have been performed. It has been suggested that lithium amide argentates such as (Me3Si)2NAg(I)Li (20) and [(Me3Si)2N]2Ag(I)Li2 (21) are formed in the reaction mixture, and the nucleophilicity and basicity of 1 are controlled by forming these species.

  DOI：

  10.1021/jo00078a024

文献信息

• Silver iodide mediated amination reaction of allylic chlorides with lithium bis(trimethylsilyl)amide: a new synthetic method of N,N-disilylallylamines via lithium amide argentates
  作者：Toshiaki Murai、Mikio Yamamoto、Shigeru Kondo、Shinzi Kato

  DOI：10.1021/jo00078a024

  日期：1993.12

  The nucleophilic substitution reaction of allylic chlorides with lithium bis(trimethylsilyl)amide (1) in the presence of silver halides has been studied in detail. Silver iodide (AgI) was found to be most effective for facilitation of the amination reaction. The reaction of alkyl-substituted allylic chlorides proceeded smoothly in S(N)2 fashion to give N,N-disilylallylamines in high yields when 0.1 or 0.5 equiv of AgI was used as an additive, whereas a stoichiometric amount of AgI was indispensable in the reaction of allylic chlorides having a phenyl group. The reaction of geranyl or neryl chloride proceeded with retention of configuration of the C=C bond to give only one isomer 4 or 5, respectively. The oxygen-containing functional groups and chlorine remained intact during the reaction. The reaction of alpha-silylmetallyl chloride 17 proceeded in an S(N)2' manner to afford (Z)-allylamine 18. So as to disclose the active species in the AgI-mediated reaction, the variable low-temperature C-13 NMR experiments using the mixture of AgI and 1 in THF have been performed. It has been suggested that lithium amide argentates such as (Me3Si)2NAg(I)Li (20) and [(Me3Si)2N]2Ag(I)Li2 (21) are formed in the reaction mixture, and the nucleophilicity and basicity of 1 are controlled by forming these species.