α-(Trimethylsilyl)crotyl chloride

• 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: α-(Trimethylsilyl)crotyl chloride
• 英文别名: (1-chloro-2-butenyl)trimethylsilane；[(E)-1-chlorobut-2-enyl]-trimethylsilane
• 化学式: C₇H₁₅ClSi
• 分子量: 162.735
• InChiKey: FISHXRKBNBZNBZ-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  α-(Trimethylsilyl)crotyl chloride 在 lithium bis(dimethylsilyl)amide 、 silver(I) iodide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 (1E,5E)-3,4-Dimethyl-1,6-bis-trimethylsilanyl-hexa-1,5-diene
  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
• 作为产物：
  描述：

  (E)-巴豆氯 、 三甲基氯硅烷 、 lithium dicyclohexylamide 以32%的产率得到
  参考文献：
  名称：

  HOSOMI, AKIRA;ANDO, MASATOMO;SAKURAI, HIDEKI, CHEM. LETT., 1984, N 8, 1385-1388

  摘要：

  DOI：

文献信息

• Copper(I) Chloride-Catalyzed Three-Component Coupling Reaction of Primary Amines with Electrophiles and α-Halogen-Substituted Allylsilanes to Form Unsymmetrical Tertiary Amines
  作者：Makoto Kozuka、Akihiko Inoue、Teruko Tsuchida、Michiharu Mitani

  DOI：10.1002/adsc.200505406

  日期：2006.5

  straightforwardly formed by the copper(I) chloride-catalyzed tandem reaction of primary amines, α-halogen-substituted allylsilanes, and electrophiles such as electron-deficient olefins, alkyl halides, alkyl tosylates, or epoxides. In the case using electron-deficient olefins as the electrophile, the addition of chloroacetone to the reaction system afforded the three-component coupling reaction more effectively

  具有三种不同取代基的叔胺（其中包括乙烯基硅烷官能团）是通过伯胺，α-卤素取代的烯丙基硅烷和亲电子试剂（例如缺电子的烯烃）的氯化铜催化串联反应直接形成的，烷基卤化物，烷基甲苯磺酸盐或环氧化物。在使用缺电子的烯烃作为亲电子试剂的情况下，向反应体系中添加氯丙酮可更有效地提供三组分偶联反应。硼酸三甲酯作为助催化剂的添加提高了使用烷基卤化物，甲苯磺酸烷基酯或环氧化物作为亲电子试剂的反应中三组分偶联产物的产率，尽管反应时间延长了。
• The Three-Component Joining Reaction of Primary Amines, Electron-Deficient Olefins, and α-Halogen-Substituted Allylsilanes Catalyzed by Copper(I) Chloride
  作者：Makoto Kozuka、Michiharu Mitani、Akihiko Inoue、Teruko Tsuchida

  DOI：10.1055/s-2004-835644

  日期：——

  Tertiary amines with three different substituents were straightforwardly obtained by the copper(I) chloride-catalyzed ­reaction of α-halogen substituted allylsilanes, electron-deficient olefins, and primary amines. This reaction was more effectively performed by the addition of chloroacetone to the reaction system.

  通过 α-卤素取代的烯丙基硅烷、缺电子烯烃和伯胺的氯化铜（I）催化反应，可以直接获得具有三个不同取代基的叔胺。通过向反应体系中加入氯丙酮，可以更有效地进行该反应。