1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-2-(thiophen-2-yl)-1-propenylidene}silanamine | 1421692-05-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-2-(thiophen-2-yl)-1-propenylidene}silanamine
• 英文别名: 1-tert-butyl-1,1-dimethyl-N-(2-(thiophen-2-yl)prop-1-en-1-ylidene)silanamine；N-(tert-butyldimethylsilyl)-2-(thiophen-2-yl)prop-1-en-1-imine；tert-butyldimethylsilylmethyl(thien-2-yl)ketene imine
• CAS: 1421692-05-8
• 化学式: C₁₃H₂₁NSSi
• 分子量: 251.468
• InChiKey: ANOFBJGCDICVLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-2-(thiophen-2-yl)-1-propenylidene}silanamine 在 (S)-3,3'-bis(2,4,6-tri-iso-propylphenyl)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate 作用下， 以 甲醇 、 甲苯 、 正戊烷 为溶剂， 反应 12.0h， 以88%的产率得到(R)-2-(thiophen-2-yl)propanenitrile
  参考文献：
  名称：

  Catalytic Asymmetric Protonation of Silyl Ketene Imines

  摘要：

  An efficient catalytic and highly enantioselective protonation of silyl ketene imines is described. The reaction is catalyzed by the chiral phosphoric acids TRIP or STRIP in the presence of a stoichiometric amount of methanol as the proton source and silyl acceptor. A variety of substituted racemic silyl ketene imines have been transformed into highly enantioenriched nitriles.

  DOI：

  10.1021/ja312141b
• 作为产物：
  描述：

  2-(thiophen-2-yl)propanenitrile 、 叔丁基二甲基氯硅烷 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 12.08h， 以80%的产率得到1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-2-(thiophen-2-yl)-1-propenylidene}silanamine
  参考文献：
  名称：

  Catalytic Asymmetric Protonation of Silyl Ketene Imines

  摘要：

  An efficient catalytic and highly enantioselective protonation of silyl ketene imines is described. The reaction is catalyzed by the chiral phosphoric acids TRIP or STRIP in the presence of a stoichiometric amount of methanol as the proton source and silyl acceptor. A variety of substituted racemic silyl ketene imines have been transformed into highly enantioenriched nitriles.

  DOI：

  10.1021/ja312141b

文献信息

• Regio- and Stereoselective Carboindation of Internal Alkynyl Ethers with Organosilicon or -stannane Nucleophiles
  作者：Kyoungmin Kang、Yoshihiro Nishimoto、Makoto Yasuda

  DOI：10.1021/acs.joc.9b01505

  日期：2019.11.1

  and reduces the activation energy. Many types of carbon nucleophiles such as silyl ketene acetals, silyl ketene imines, a silyl cyanide, an alkynyl stannane, and an allylic stannane were applicable to the present reaction system to give highly functionalized metalated enol ethers (β-alkoxyalkenylindiums). The prepared β-alkoxyalkenylindiums were transformed to various functionalized tetrasubstituted

  我们使用InI3和有机硅或-锡烷亲核试剂合成（Z）-β-烷氧基烯基铟，实现了末端和内部炔基醚的区域和立体选择性碳氢化。通过（Z）-β-烷氧基烯基铟产物的X射线衍射分析证实，碳金属化区域和立体选择性地以抗加成方式进行。与计算炔基醚的碳类似物并行地进行了关于炔基醚的碳键化以阐明烷氧基的作用的理论计算。碳偶合反应的反应曲线和计算数据表明，烷氧基增强了InI3和炔烃部分之间的相互作用，并降低了活化能。许多类型的碳亲核试剂，例如甲硅烷基乙烯酮缩醛，甲硅烷基乙烯酮亚胺，甲硅烷基氰化物，炔基锡烷和烯丙基锡烷可用于本反应体系，以得到高度官能化的金属化烯醇醚（β-烷氧基烯基铟）。通过碘化然后铃木偶联将制备的β-烷氧基烯基铟转化成各种官能化的四取代的烯醇醚。含有酚醚部分的七元环化合物的合成是使用包括本发明的立体选择性碳indindation的顺序过程完成的。
• Indium Tribromide Catalyzed Coupling Reaction of Enol Ethers with Silyl Ketene Imines toward the Synthesis of β,γ-Unsaturated Nitriles
  作者：Yoshihiro Nishimoto、Takashi Nishimura、Makoto Yasuda

  DOI：10.1002/chem.201503414

  日期：2015.12.7

  Herein, a coupling reaction of enol ethers with silyl ketene imines in the presence of catalytic amounts of InBr3 and Me3SiBr is described. Kinetic studies have revealed that an indium catalyst and Me3SiBr accelerated the coupling process and the regeneration of the catalyst, respectively. Various types of enol ethers and silyl ketene imines are applicable. In addition, a formal synthesis of verapamil

  在此，描述了在催化量的InBr 3和Me 3 SiBr存在下烯醇醚与甲硅烷基烯酮亚胺的偶联反应。动力学研究表明，铟催化剂和Me 3 SiBr分别加速了偶联过程和催化剂的再生。各种类型的烯醇醚和甲硅烷基烯酮亚胺是适用的。另外，通过使用这种新颖的偶联反应，完成了维拉帕米的正式合成。
• Enantioselective Construction of Vicinal Tetrasubstituted Stereocenters by the Mannich Reaction of Silyl Ketene Imines with Isatin‐Derived Ketimines
  作者：Jiannan Zhao、Bing Fang、Weiwei Luo、Xiaoyu Hao、Xiaohua Liu、Lili Lin、Xiaoming Feng

  DOI：10.1002/anie.201408730

  日期：2015.1.2

  A highly enantioselective Mannich reaction of silyl ketene imines with isatin‐derived ketimines has been realized by using a chiral N,N′‐dioxide/ZnII catalyst. A variety of β‐amino nitriles containing congested vicinal tetrasubstituted stereocenters were obtained with excellent outcomes (up to 98 % yield, >19:1 d.r. and 99 % ee). Based on the experimental investigations, a possible transition state

  通过使用手性N，N'-二氧化物/ Zn II催化剂，实现了甲硅烷基烯酮亚胺与异麦芽酮酮酮的高度对映选择性曼尼希反应。获得了多种包含拥挤的邻近四取代立体中心的β-氨基腈，具有优异的结果（产率高达98％，dr> 19：1，ee高达99％  ）。根据实验研究，提出了一种可能的过渡态来解释不对称感应的起源。
• <i>Anti</i>-Carboalumination of Alkynes Using Aluminum Trihalide and Silyl Ketene Imines: Stereo- and Regioselective Synthesis of Alkenylaluminum Compounds Bearing a Cyano Group
  作者：Yoshihiro Nishimoto、Rina Hirase、Makoto Yasuda

  DOI：10.1021/acs.orglett.8b01371

  日期：2018.6.15

  An organoaluminum-free and catalyst-free anti-carboalumination of alkynes using aluminum trihalides and silyl ketene imines was developed. Three components, an alkyne, AlX3, and a silyl ketene imine, were simply mixed to give the alkenylaluminum bearing a cyano group with regioselectivity. Theoretical calculations revealed the effective activation of the alkyne by AlX3 to enhance the regioselective carboalumination. The synthesized alkenylaluminums were applicable to many organic transformations.