ethyl 6-methyl-3-phenyl-2H-1,4-oxazine-5-carboxylate | 1198359-03-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 6-methyl-3-phenyl-2H-1,4-oxazine-5-carboxylate
• CAS: 1198359-03-3
• 化学式: C₁₄H₁₅NO₃
• 分子量: 245.278
• InChiKey: FFZOOKYKYMAQMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  重氮基乙酰乙酸乙酯 、 3-phenyl-2H-azirine 在 rhodium(II) acetate dimer 作用下， 以 1,1-二氯乙烷 为溶剂， 以73%的产率得到ethyl 6-methyl-3-phenyl-2H-1,4-oxazine-5-carboxylate
  参考文献：
  名称：

  Rh(II)-Catalysed reactions of 2H-azirines with ethyl 2-acyl-2-diazoacetates. Synthesis of novel photochromic oxazines

  摘要：

  Photochromic non-fused 2H-1,4-oxazines are synthesised by a Rh-2(OAc)(4)-catalysed reaction of 2H-azirines with ethyl 2-acyl-2-diazoacetates. The reaction proceeds via the formation of an azirinium ylide which undergoes ring-opening to a 2-azadiene followed by 1,6-electrocyclisation (C) 2009 Elsevier Ltd All lights reserved

  DOI：

  10.1016/j.tetlet.2009.09.033

文献信息

• Copper-catalyzed condensation of imines and α-diazo-β-dicarbonyl compounds: modular and regiocontrolled synthesis of multisubstituted pyrroles
  作者：Wei Wen Tan、Naohiko Yoshikai

  DOI：10.1039/c5sc02322j

  日期：——

  In the presence of a copper(II) catalyst, enolizable imines bearing various N-substituents and α-diazo-β-ketoesters undergo denitrogenative and dehydrative condensation to afford highly substituted pyrroles in moderate to good yields with exclusive regioselectivity. The reaction likely involves nucleophilic addition of the imine nitrogen to a copper carbenoid, tautomerization of the resulting azomethine

  在铜（II）催化剂的存在下，带有各种N-取代基和α-重氮-β-酮酸酯的可烯醇化的亚胺进行脱氮和脱水缩合反应，以中等至良好的收率得到高度取代的吡咯，具有唯一的区域选择性。该反应可能涉及将亚胺氮亲核加成至铜类胡萝卜素，将所得的甲亚胺叶立德互变异构成α-烯酮，以及随后的烯胺-酮环缩合。与Yb（OTf）3作为独特的助催化剂，α-重氮-β-二酮也参与相同的缩合反应。本反应适用于具有宽泛的官能团和杂环部分耐受性的无环，环外和环内亚胺，从而为合成天然产物lamellarin家族开辟了一条新的便利途径。
• Rh(II)-carbenoid mediated 2H-azirine ring-expansion as a convenient route to non-fused photo- and thermochromic 2H-1,4-oxazines
  作者：Nikolai V. Rostovskii、Mikhail S. Novikov、Alexander F. Khlebnikov、Vsevolod A. Khlebnikov、Sergei M. Korneev

  DOI：10.1016/j.tet.2013.03.106

  日期：2013.5

  The Rh2(OAc)(4)-catalyzed domino reaction of 2H-azirines with 2-acyl-2-diazoacetates provides a unique synthetic approach to non-fused 2H-1,4-oxazines. The reaction proceeds via sequential formation of a rhodium carbenoid, an azirinium ylide, and a 1-acyl-1-(alkoxycarbonyl)-2-azabuta-1,3-diene to give, after 1,6-pi-electrocyclization, a 2H-1,4-oxazine derivative in good yield. The observed stereoselectivity of 2-azadiene formation is consistent with DFT calculations of the azirinium ylide-2-azadiene isomerization, providing evidence for the ylide mechanism of the reaction. The substitution pattern and configuration of the carbon carbon double bond in 2-azadienes has a dramatic influence on their cyclization to oxazines: the CO2R group on C-4 stabilizes an open-chain form and, as the result of this, a new class of stable 2-azadienes, 1-acyl-2-azadiene-1,4-dicarboxylates, could be isolated. The 1,4-oxazines obtained by this method are the first representatives of monocyclic 2H-1,4-oxazine derivatives, which exhibit photo- and thermochromic activity. (C) 2013 Elsevier Ltd. All rights reserved.