(3-phenylallylidene)(trimethylsilanyl)amine | 96735-58-9

• 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: (3-phenylallylidene)(trimethylsilanyl)amine
• 英文别名: TMS-N=CH-CH=CH-Ph；3-Phenyl-N-(trimethylsilyl)prop-2-en-1-imine；3-phenyl-N-trimethylsilylprop-2-en-1-imine
• CAS: 96735-58-9
• 化学式: C₁₂H₁₇NSi
• 分子量: 203.359
• InChiKey: UPNZTQPIGQXGGQ-UHFFFAOYSA-N

物化性质

• 沸点：
  272.7±33.0 °C(Predicted)
• 密度：
  0.85±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  β-溴苯乙烯 、 (3-phenylallylidene)(trimethylsilanyl)amine 在 tris(dibenzylideneacetone)dipalladium (0) sodium t-butanolate 、 2-二环己膦基-2'-(N,N-二甲胺)-联苯 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以93%的产率得到N-(3-phenylallylidene)styrylamine
  参考文献：
  名称：

  N-三烷基甲硅烷基亚胺作为钯催化C [N]形成反应的偶联伴侣：由芳基和烯基溴化物一步合成亚胺和氮杂二烯。

  摘要：

  DOI：

  10.1002/anie.200352808
• 作为产物：
  描述：

  三甲基氯硅烷 、 肉桂醛 在 lithium hexamethyldisilazane 作用下， 生成 (3-phenylallylidene)(trimethylsilanyl)amine
  参考文献：
  名称：

  甲硅烷基乙烯酮缩醛与N-三甲基甲硅烷基亚胺的反应：一条通往N-未取代的氮杂环丁烷-2-酮的途径

  摘要：

  在ZnI 2和叔丁醇存在下，N-三甲基甲硅烷基亚胺与甲硅烷基烯酮缩醛反应，然后用MeMgBr原位处理中间的N-甲硅烷基β-氨基酯，生成N-未取代的氮杂环丁烷-2-酮良品率高。

  DOI：

  10.1039/c39850000539

文献信息

• A new route to silyl-substituted cyclobutenones and silylketenes
  作者：Konstantin Benda、Tanja Knoth、Rick L. Danheiser、Ernst Schaumann

  DOI：10.1016/j.tetlet.2010.10.130

  日期：2011.1

  2-Silyl-cyclobutene(di)ones are obtained by an addition/substitution approach on dimethyl squarate using silyl anions. The acetal and in particular the thioacetal derivatives readily undergo electrocyclic ring opening to reactive silyl(vinyl)ketenes.

  2-甲硅烷基-环丁烯（二）酮是通过使用甲硅烷基阴离子对方酸二甲酯的加成/取代方法获得的。缩醛，特别是硫代缩醛衍生物，容易进行电环开环，生成反应性甲硅烷基（乙烯基）烯酮。
• An easy synthesis of electron-withdrawing substituted 2-aza-1,3-dienes and their 1,4-cycloaddition with enamines
  作者：José Barluenga、Miguel Tomás、Alfredo Ballesteros、Vicente Gotor

  DOI：10.1039/c39870001195

  日期：——

  An easy procedure for the synthesis of electron-poor 2-aza-1,3-dienes from silylimines is described; the ability of these azadienes to undergo cycloaddition to electron-rich alkenes is demonstrated for the first time.

  描述了一种从水飞蓟宾合成贫电子的2-氮杂-1,3-二烯的简便方法。这些氮杂二烯进行环加成成富电子烯烃的能力首次得到证明。
• Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals
  作者：Yi Wei、Xiao‐Yu Xie、Jiabin Liu、Xiaoxiao Liu、Bo Zhang、Xin‐Yi Chen、Shi‐Jun Li、Yu Lan、Kai Hong

  DOI：10.1002/anie.202401050

  日期：2024.4.24

  Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron‐containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates.
• N-Trialkylsilylimines as Coupling Partners for Pd-Catalyzed CN Bond-Forming Reactions: One-Step Synthesis of Imines and Azadienes from Aryl and Alkenyl Bromides
  作者：José Barluenga、Fernando Aznar、Carlos Valdés

  DOI：10.1002/anie.200352808

  日期：2004.1.5
• Reaction of silyl ketene acetals with N-trimethylsilyl imines: a route to N-unsubstituted azetidin-2-ones
  作者：Ernest W. Colvin、Daniel G. McGarry

  DOI：10.1039/c39850000539

  日期：——

  Reaction of N-trimethylsilyl imines with silyl ketene acetals in the presence of ZnI2 and t-butyl alcohol, followed by treatment in situ of the intermediate N-silyl β-aminoesters with MeMgBr, leads to N-unsubstituted azetidin-2-ones in good yield.

  在ZnI 2和叔丁醇存在下，N-三甲基甲硅烷基亚胺与甲硅烷基烯酮缩醛反应，然后用MeMgBr原位处理中间的N-甲硅烷基β-氨基酯，生成N-未取代的氮杂环丁烷-2-酮良品率高。