3,4-dihydro-7,8-dimethoxyisocoumarin | 91143-60-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 3,4-dihydro-7,8-dimethoxyisocoumarin
• 英文别名: 7,8-dimethoxyisochroman-1-one；7,8-Dimethoxy-3,4-dihydro-isocumarin；7,8-Dimethoxy-3,4-dihydroisochromen-1-one
• CAS: 91143-60-1
• 化学式: C₁₁H₁₂O₄
• 分子量: 208.214
• InChiKey: PXHREPVVDJTKQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  7,8-dimethoxyisochroman 在 iron(II) triflate 、 2-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)-6-((4R,5R)-1-((4-(tert-butyl)phenyl)sulfonyl)-4,5-diphenylimidazolidin-2-yl)pyridine 、 氧气 作用下， 以 苯 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 以8%的产率得到3,4-dihydro-7,8-dimethoxyisocoumarin
  参考文献：
  名称：

  Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst

  摘要：

  Selective alpha-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective alpha-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O-2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H-2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O-2 into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H-2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts.

  DOI：

  10.1021/ja502167h

文献信息

• Napolitano, Elio; Morsani, Massimo; Fiaschi, Rita, Gazzetta Chimica Italiana, 1991, vol. 121, # 5, p. 249 - 255
  作者：Napolitano, Elio、Morsani, Massimo、Fiaschi, Rita

  DOI：——

  日期：——
• NAPOLITANO, ELIO;MORSANI, MASSIMO;FIASCHI, RITA, GAZZ. CHIM. ITAL., 121,(1991) N, C. 249-255
  作者：NAPOLITANO, ELIO、MORSANI, MASSIMO、FIASCHI, RITA

  DOI：——

  日期：——
• Dehydrogenative α-Oxygenation of Ethers with an Iron Catalyst
  作者：Angela Gonzalez-de-Castro、Craig M. Robertson、Jianliang Xiao

  DOI：10.1021/ja502167h

  日期：2014.6.11

  Selective alpha-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective alpha-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O-2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H-2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O-2 into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H-2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts.