1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-(4-methoxyphenyl)-1-propenylidene}silanamine | 960595-40-8

• 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: 1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-(4-methoxyphenyl)-1-propenylidene}silanamine
• 英文别名: 1-(1,1-dimethylethyl)-N-[2-(4-methoxyphenyl)-1-propenylidene]-1,1-dimethylsilanamine；1-tert-butyl-N-(2-(4-methoxyphenyl)prop-1-en-1-ylidene)-1,1-dimethylsilanamine
• CAS: 960595-40-8
• 化学式: C₁₆H₂₅NOSi
• 分子量: 275.466
• InChiKey: FDOPVVKIKMUWTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-(4-methoxyphenyl)-1-propenylidene}silanamine 在 (Ra)-12-hydroxy-1,10-bis(2,4,6-triisopropylphenyl)-4,5,6,7-tetrahydrodiindeno[1,3,2]dioxaphosphocine 12-oxide 作用下， 以 甲醇 、 甲苯 、 正戊烷 为溶剂， 反应 12.0h， 以82%的产率得到(S)-2-(4-methoxyphenyl)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-(4-methoxyphenyl)propionitrile 、 叔丁基二甲基氯硅烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.08h， 生成 1-(1,1-dimethylethyl)-1,1-dimethyl-N-{2-(4-methoxyphenyl)-1-propenylidene}silanamine
  参考文献：
  名称：

  通过路易斯碱催化甲硅烷基乙烯酮亚胺与醛的加成对四元立体碳的对映选择性构建

  摘要：

  衍生自各种α-支化腈的甲硅烷基乙烯酮亚胺已被开发为非常有用的试剂，用于通过醛醇加成反应构建四元立体中心。在 SiCl4 存在和手性磷酰胺 (R,R)-5 的催化作用下，甲硅烷基乙烯酮亚胺以极快的速度和高产率添加到各种芳香醛中，并具有出色的非对映选择性和对映选择性。特别值得注意的是从富电子、缺电子和受阻醛中获得的高产率和选择性。腈功能可作为进一步合成操作的有用前体。

  DOI：

  10.1021/ja077134y

文献信息

• 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 Quaternary Stereogenic Carbons by the Lewis Base Catalyzed Additions of Silyl Ketene Imines to Aldehydes
  作者：Scott E. Denmark、Tyler W. Wilson、Matthew T. Burk、John R. Heemstra

  DOI：10.1021/ja077134y

  日期：2007.12.1

  Silyl ketene imines derived from a variety of alpha-branched nitriles have been developed as highly useful reagents for the construction of quaternary stereogenic centers via the aldol addition reaction. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-5, silyl ketene imines undergo extremely rapid and high yielding addition to a wide variety of aromatic aldehydes with

  衍生自各种α-支化腈的甲硅烷基乙烯酮亚胺已被开发为非常有用的试剂，用于通过醛醇加成反应构建四元立体中心。在 SiCl4 存在和手性磷酰胺 (R,R)-5 的催化作用下，甲硅烷基乙烯酮亚胺以极快的速度和高产率添加到各种芳香醛中，并具有出色的非对映选择性和对映选择性。特别值得注意的是从富电子、缺电子和受阻醛中获得的高产率和选择性。腈功能可作为进一步合成操作的有用前体。
• 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。
• Asymmetric Synthesis of β-Amino Nitriles through a Sc^III-Catalyzed Three-Component Mannich Reaction of Silyl Ketene Imines
  作者：Jiannan Zhao、Xiaohua Liu、Weiwei Luo、Mingsheng Xie、Lili Lin、Xiaoming Feng

  DOI：10.1002/anie.201209093

  日期：2013.3.18

  containing contiguous tertiary and quaternary stereogenic carbon centers were synthesized by using the title reaction. The reaction was catalyzed by a chiral N,N′‐dioxide scandium(III) complex under mild reaction conditions. Based on experimental investigations, a possible transition state has been proposed to explain the origin of asymmetric inductivity.

  使用标题反应合成了一系列包含连续的叔碳立体中心和季碳立体中心的β-氨基腈。在温和的反应条件下，该反应由手性N，N'-二氧化scan（III）配合物催化。在实验研究的基础上，提出了一种可能的过渡态来解释非对称电感性的起源。
• Catalytic Asymmetric Protonation of Silyl Ketene Imines
  作者：Joyram Guin、Georgy Varseev、Benjamin List

  DOI：10.1021/ja312141b

  日期：2013.2.13

  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.