methyl 3-(4-cyanophenyl)-2-diazo-3-oxopropanoate | 1431935-08-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: methyl 3-(4-cyanophenyl)-2-diazo-3-oxopropanoate
• 英文别名: (Z)-1-(4-cyanophenyl)-2-diazonio-3-methoxy-3-oxoprop-1-en-1-olate
• CAS: 1431935-08-8
• 化学式: C₁₁H₇N₃O₃
• 分子量: 229.195
• InChiKey: GCDJABOWDZPFME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  69.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-(4-cyanophenyl)-2-diazo-3-oxopropanoate 在 dirhodium tetraacetate 、 RhCl[(R,R)-TsDPEN](C5Me5) 、 氨基磺酰氯 、 水 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 N,N-二甲基乙酰胺 、 乙酸乙酯 、 甲苯 为溶剂， 反应 3.0h， 生成 methyl (4S,5S)-4-(4-cyanophenyl)-1,2,3-oxathiazolidine-5-carboxylate 2,2-dioxide
  参考文献：
  名称：

  Stereoselective synthesis of 4-substituted-cyclic sulfamidate-5-carboxylates by asymmetric transfer hydrogenation accompanied by dynamic kinetic resolution and applications to concise stereoselective syntheses of (−)-epi-cytoxazone and the taxotere side-chain

  摘要：

  DKR驱动的不对称转移氢化反应已经成功开发，用于环状磺胺酸酯亚胺-5-羧酸酯。

  DOI：

  10.1039/c4cc06395c
• 作为产物：
  描述：

  3-(4-氰基-苯基)-3-氧代-丙酸甲酯 在 对甲苯磺酰叠氮 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 生成 methyl 3-(4-cyanophenyl)-2-diazo-3-oxopropanoate
  参考文献：
  名称：

  Stereoselective synthesis of 4-substituted-cyclic sulfamidate-5-carboxylates by asymmetric transfer hydrogenation accompanied by dynamic kinetic resolution and applications to concise stereoselective syntheses of (−)-epi-cytoxazone and the taxotere side-chain

  摘要：

  DKR驱动的不对称转移氢化反应已经成功开发，用于环状磺胺酸酯亚胺-5-羧酸酯。

  DOI：

  10.1039/c4cc06395c

文献信息

• 4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles
  作者：Ilia A. Smetanin、Mikhail S. Novikov、Nikolai V. Rostovskii、Alexander F. Khlebnikov、Galina L. Starova、Dmitry S. Yufit

  DOI：10.1016/j.tet.2015.05.022

  日期：2015.7

  A wide range of electron-poor 4-bromo-/4-chloro-2-azabuta-1,3-dienes were synthesized by the Rh-2(OAc)(4)-catalyzed reaction of diazo esters and diazo ketones with methyl 2-halo-2H-azirine-2-carboxylates. The E stereoselectivity with respect to the configuration of the C=C bond of the 2-azadiene moiety is in good agreement with the results of DFT (M06-2X/6-31+G(d,p)) calculations of the reaction pathway. The reaction proceeds via the formation of an azirinium ylide intermediate followed by ring opening with outward rotation of the halogen atom. Depending on the substitution pattern at C-1 electron-poor 4-halo-2-azabutadienes can undergo two types of cyclization at elevated temperatures: reversible 1,4-electrocyclization to give 2,3-dihydroazetes or 1,5-exo-trig cyclization to give 5-methylene-2,5-dihydrooxazoles, both in good yields. The dihydrooxazole derivatives can be also obtained at ambient temperature under DBU catalysis. (C) 2015 Elsevier Ltd. All rights reserved.
• 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.