N-phenylmethyl-[2-(trimethylsilyl)ethyl]-N-vinylcarbamate | 221325-25-3

• 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: N-phenylmethyl-[2-(trimethylsilyl)ethyl]-N-vinylcarbamate
• 英文别名: 2-trimethylsilylethyl N-benzyl-N-ethenylcarbamate
• CAS: 221325-25-3
• 化学式: C₁₅H₂₃NO₂Si
• 分子量: 277.439
• InChiKey: JWFVVVQNZFEXEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-phenylmethyl-[2-(trimethylsilyl)ethyl]-N-vinylcarbamate 在 四丁基氟化铵 作用下， 以 乙腈 为溶剂， 反应 16.0h， 生成 (2RS,3RS)-2-phenyl-3-[(phenylmethyl)amino]oxetane
  参考文献：
  名称：

  Photocycloaddition of N-Acyl Enamines to Aldehydes and Its Application to the Synthesis of Diastereomerically Pure 1,2-Amino Alcohols

  摘要：

  The regio- and stereoselective synthesis of the protected cis-3-aminooxetanes cis-5 and cis-7 is reported. The oxetanes were obtained by the photocycloaddition of aliphatic (6c-e) and aromatic (4, 6a) aldehydes to the corresponding enamides (1a-d,h) or enecarbamates (le-g). The enamine derivatives used in the Paterno-Buchi reaction were either commercially available or prepared from the corresponding acetaldehyde imines 2 by acylation. The oxetane formation proceeded with good-to-excellent simple diastereoselectivity for aromatic aldehydes (56-82% yield) and moderate selectivity for aliphatic aldehydes (46-55% yield). The cis-3-aminooxetanes are precursors for syn- and anti-1,2-amino alcohols. The relative configuration established in the photochemical step was retained upon nucleophilic ring opening between the oxygen atom and carbon atom C-4. By this means, syn-1,2-amino alcohols such as 8 and 10 were available in good yields. In contrast, the N-Boc-protected cis-3-aminooxetanes cis-5e and cis-5f were transformed into anti-1,2-amino alcohols. Upon treatment with trifluoroacetic acid, they underwent an intramolecular nucleophilic substitution at the carbon atom C-2 of the oxetane and the oxazolidinones II and 12 were formed. Because the substitution occurs with inversion of configuration, anti-1,2-amino alcohols, e.g., ephedrine (15), are accessible.

  DOI：

  10.1021/jo9819988
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 、 N-benzyl-N-vinylcarbamoyl chloride 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 以95%的产率得到N-phenylmethyl-[2-(trimethylsilyl)ethyl]-N-vinylcarbamate
  参考文献：
  名称：

  Photocycloaddition of N-Acyl Enamines to Aldehydes and Its Application to the Synthesis of Diastereomerically Pure 1,2-Amino Alcohols

  摘要：

  The regio- and stereoselective synthesis of the protected cis-3-aminooxetanes cis-5 and cis-7 is reported. The oxetanes were obtained by the photocycloaddition of aliphatic (6c-e) and aromatic (4, 6a) aldehydes to the corresponding enamides (1a-d,h) or enecarbamates (le-g). The enamine derivatives used in the Paterno-Buchi reaction were either commercially available or prepared from the corresponding acetaldehyde imines 2 by acylation. The oxetane formation proceeded with good-to-excellent simple diastereoselectivity for aromatic aldehydes (56-82% yield) and moderate selectivity for aliphatic aldehydes (46-55% yield). The cis-3-aminooxetanes are precursors for syn- and anti-1,2-amino alcohols. The relative configuration established in the photochemical step was retained upon nucleophilic ring opening between the oxygen atom and carbon atom C-4. By this means, syn-1,2-amino alcohols such as 8 and 10 were available in good yields. In contrast, the N-Boc-protected cis-3-aminooxetanes cis-5e and cis-5f were transformed into anti-1,2-amino alcohols. Upon treatment with trifluoroacetic acid, they underwent an intramolecular nucleophilic substitution at the carbon atom C-2 of the oxetane and the oxazolidinones II and 12 were formed. Because the substitution occurs with inversion of configuration, anti-1,2-amino alcohols, e.g., ephedrine (15), are accessible.

  DOI：

  10.1021/jo9819988

文献信息

• Paternò-Büchi Reactions of Silyl Enol Ethers and Enamides
  作者：Thorsten Bach、Florian Vogt、Kai Jödicke、Jürgen Schröder

  DOI：10.1055/s-0029-1217095

  日期：——

  aromatic aldehydes and silyl enol ethers in benzene as the solvent. The reactions occur with high simple diastereoselectivity and, when R¹ is chiral, with high facial diastereoselectivity. Under similar conditions, but in acetonitrile rather than benzene as the preferred solvent, the Paternò-Büchi reaction of N-acyl enamines (enamides) gives the corresponding protected 3-aminooxetanes. The cis-products

  3-（甲硅烷氧基）氧杂环丁烷是通过将芳族醛和甲硅烷基烯醇醚的混合物辐照在作为溶剂的苯中获得的。反应以高的简单非对映选择性发生，而当R 1为手性时，则以高的面部非对映选择性发生。在相似的条件下，但在乙腈而不是苯中作为优选溶剂，N-酰基烯胺（酰胺）的Paternò-Büchi反应得到相应的保护的3-氨基氧杂环丁烷。获得的顺式产物具有明显的简单非对映选择性。 环加成-杂环-氧杂环丁烷-帕特诺-布奇反应-光化学
• Photocycloaddition of <i>N</i>-Acyl Enamines to Aldehydes and Its Application to the Synthesis of Diastereomerically Pure 1,2-Amino Alcohols
  作者：Thorsten Bach、Jürgen Schröder

  DOI：10.1021/jo9819988

  日期：1999.2.1

  The regio- and stereoselective synthesis of the protected cis-3-aminooxetanes cis-5 and cis-7 is reported. The oxetanes were obtained by the photocycloaddition of aliphatic (6c-e) and aromatic (4, 6a) aldehydes to the corresponding enamides (1a-d,h) or enecarbamates (le-g). The enamine derivatives used in the Paterno-Buchi reaction were either commercially available or prepared from the corresponding acetaldehyde imines 2 by acylation. The oxetane formation proceeded with good-to-excellent simple diastereoselectivity for aromatic aldehydes (56-82% yield) and moderate selectivity for aliphatic aldehydes (46-55% yield). The cis-3-aminooxetanes are precursors for syn- and anti-1,2-amino alcohols. The relative configuration established in the photochemical step was retained upon nucleophilic ring opening between the oxygen atom and carbon atom C-4. By this means, syn-1,2-amino alcohols such as 8 and 10 were available in good yields. In contrast, the N-Boc-protected cis-3-aminooxetanes cis-5e and cis-5f were transformed into anti-1,2-amino alcohols. Upon treatment with trifluoroacetic acid, they underwent an intramolecular nucleophilic substitution at the carbon atom C-2 of the oxetane and the oxazolidinones II and 12 were formed. Because the substitution occurs with inversion of configuration, anti-1,2-amino alcohols, e.g., ephedrine (15), are accessible.