2-(Dimethoxymethyl)-3-phenyl-2H-azirin | 56900-68-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 叠氮烷
• 英文名称: 2-(Dimethoxymethyl)-3-phenyl-2H-azirin
• 英文别名: 3-Phenyl-2-(dimethoxymethyl)-azirin；2-dimethoxymethyl-3-phenyl-2H-azirine；2-(dimethoxymethyl)-3-phenyl-2H-azirene；2-(dimethoxymethyl)-3-phenyl-2H-azirine
• CAS: 56900-68-6
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: XHJMEPOZUBIUBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(Dimethoxymethyl)-3-phenyl-2H-azirin 、 重氮基乙酰乙酸乙酯 在 dirhodium tetraacetate 作用下， 以 1,2-二氯乙烷 为溶剂， 以28%的产率得到ethyl 2-(dimethoxymethyl)-6-methyl-3-phenyl-2H-1,4-oxazine-5-carboxylate
  参考文献：
  名称：

  Rh2(OAc)4-catalyzed reaction of α-diazocarbonyl compounds with 2-carbonyl-substituted 2H-azirines

  摘要：

  The Rh-2(OAc)(4)-catalyzed reaction of 2H-azirine-2-carbaldehydes with dimethyl diazomalonate proceeds via azirinium ylide formation, isomerization to 2-azabuta-1,3-dienes followed by 1,6-pi-electrocyclization to give 2H-1,3-oxazines. According to DFT-calculations ring opening of azirinium ylides should occur stereoselectively to give 2-azadienes with the C=C bond exclusively in the Z configuration. Changing a formyl group for an acetyl group in the azirine leads to a lowering of stereoselectivity and the formation of azadienes with an E configuration of the C=C bond was observed. The reaction of 2-acy1-2-diazoacetates with 2H-azirine-2-carbaldehydes proceeds similarly, but the 2-acetyl-substituted 2H-1,3-oxazines formed are unstable under chromatographic purification and rearrange easily into pyrrole derivatives. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.022

文献信息

• Rh2(OAc)4-catalyzed reaction of α-diazocarbonyl compounds with 2-carbonyl-substituted 2H-azirines
  作者：Kirill V. Zavyalov、Mikail S. Novikov、Alexander F. Khlebnikov、Dmitry S. Yufit

  DOI：10.1016/j.tet.2013.04.022

  日期：2013.6

  The Rh-2(OAc)(4)-catalyzed reaction of 2H-azirine-2-carbaldehydes with dimethyl diazomalonate proceeds via azirinium ylide formation, isomerization to 2-azabuta-1,3-dienes followed by 1,6-pi-electrocyclization to give 2H-1,3-oxazines. According to DFT-calculations ring opening of azirinium ylides should occur stereoselectively to give 2-azadienes with the C=C bond exclusively in the Z configuration. Changing a formyl group for an acetyl group in the azirine leads to a lowering of stereoselectivity and the formation of azadienes with an E configuration of the C=C bond was observed. The reaction of 2-acy1-2-diazoacetates with 2H-azirine-2-carbaldehydes proceeds similarly, but the 2-acetyl-substituted 2H-1,3-oxazines formed are unstable under chromatographic purification and rearrange easily into pyrrole derivatives. (C) 2013 Elsevier Ltd. All rights reserved.