(E)-ethylidenetrimethylsilylmethylamine | 883627-58-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-ethylidenetrimethylsilylmethylamine
• 英文别名: (E)-N-(trimethylsilylmethyl)ethanimine
• CAS: 883627-58-5
• 化学式: C₆H₁₅NSi
• 分子量: 129.277
• InChiKey: GREYJWPPUYZLTI-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2-(4(S)-phenyloxazolidin-2-on-3-yl)acetyl chloride 、 (E)-ethylidenetrimethylsilylmethylamine 以28%的产率得到N-(trimethylsilyl)methyl-N-vinyl-((4S)-2-oxo-4-phenyloxazolidin-3-yl)acetamide
  参考文献：
  名称：

  A Contribution to the Asymmetric Synthesis of 3-Amino β-Lactams: The Diastereoselective [2+2] Cycloaddition Reaction of Chiral Aminoketene Equivalents with Enolizable Aldehyde-Derived Imines

  摘要：

  AbstractN‐[Bis(trimethylsilyl)methyl]imines 9 show unique chemical properties when compared with conventional imines. Their reaction with optically pure aminoketenes derived from dehydrochlorination of 14 and 15 affords the corresponding 3‐amino‐4‐alkyl‐β‐lactams 16 and 17 in good yields and high diastereoselectivities. The mild deprotection of bis(trimethylsilyl)methyl‐ and phenyloxazolidinone moieties with, respectively, cerium(IV) ammonium nitrate and lithium/ammonia or hydrogen/Pd(OH)2 allows the preparation of a variety of β‐lactam antibiotic building blocks.

  DOI：

  10.1002/chem.19970030909
• 作为产物：
  描述：

  N-trimethylsilylmethyl P-trimethyl-λ⁵-phosphazene 、 乙醛 以 氯仿 为溶剂， 反应 0.02h， 生成 (E)-ethylidenetrimethylsilylmethylamine
  参考文献：
  名称：

  磷酸和醛类之间的Aza-Wittig反应的机理和立体选择性

  摘要：

  使用DFT方法（B3LYP / 6-31G *级）并通过实验对磷腈与醛之间的aza-Wittig反应机理进行了计算研究。已经发现反应由串联的[2 + 2]环加成-环还原序列组成，其中涉及π和σ轨道以及孤对。既[2 + 2]流程经由热允许同上发生-同上机制。P -三甲基- λ 5个-phosphazenes被预测为比它们的反应性更强P -三苯基类似物。整个反应的立体化学结果仅取决于第二步骤中，因为在中间1,3,2-λ构象变化5-草氮磷氮杂环丁烷的活化能比第二个[2 + 2]环还原反应低得多。预测了相应的（E）-亚胺的优先或排他性形成。

  DOI：

  10.1021/jo0525884

文献信息

• A Contribution to the Asymmetric Synthesis of 3-Amino β-Lactams: The Diastereoselective [2+2] Cycloaddition Reaction of Chiral Aminoketene Equivalents with Enolizable Aldehyde-Derived Imines
  作者：Claudio Palomo、Jesus M. Aizpurua、Marta Legido、Antonia Mielgo、Regina Galarza

  DOI：10.1002/chem.19970030909

  日期：1997.9

  AbstractN‐[Bis(trimethylsilyl)methyl]imines 9 show unique chemical properties when compared with conventional imines. Their reaction with optically pure aminoketenes derived from dehydrochlorination of 14 and 15 affords the corresponding 3‐amino‐4‐alkyl‐β‐lactams 16 and 17 in good yields and high diastereoselectivities. The mild deprotection of bis(trimethylsilyl)methyl‐ and phenyloxazolidinone moieties with, respectively, cerium(IV) ammonium nitrate and lithium/ammonia or hydrogen/Pd(OH)2 allows the preparation of a variety of β‐lactam antibiotic building blocks.
• Mechanism and Stereoselectivity of the Aza-Wittig Reaction between Phosphazenes and Aldehydes
  作者：Fernando P. Cossío、Concepción Alonso、Begoña Lecea、Mirari Ayerbe、Gloria Rubiales、Francisco Palacios

  DOI：10.1021/jo0525884

  日期：2006.3.31

  The mechanism of the aza-Wittig reaction between phosphazenes and aldehydes has been studied computationally, using DFT methods (B3LYP/6-31G* level), and experimentally. It has been found that the reaction consists of a tandem [2+2] cycloaddition−cycloreversion sequence in which π and σ orbitals as well as lone pairs are involved. Both [2+2] processes take place via thermally allowed supra-supra mechanisms

  使用DFT方法（B3LYP / 6-31G *级）并通过实验对磷腈与醛之间的aza-Wittig反应机理进行了计算研究。已经发现反应由串联的[2 + 2]环加成-环还原序列组成，其中涉及π和σ轨道以及孤对。既[2 + 2]流程经由热允许同上发生-同上机制。P -三甲基- λ 5个-phosphazenes被预测为比它们的反应性更强P -三苯基类似物。整个反应的立体化学结果仅取决于第二步骤中，因为在中间1,3,2-λ构象变化5-草氮磷氮杂环丁烷的活化能比第二个[2 + 2]环还原反应低得多。预测了相应的（E）-亚胺的优先或排他性形成。