3,4-dihydro-3-methyl-1H-benzopyran-5,8-dione | 82301-13-1

• 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-3-methyl-1H-benzopyran-5,8-dione
• 英文别名: 3-methyl-3,4-dihydro-1H-isochromene-5,8-dione
• CAS: 82301-13-1
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: LNMCLPWJLBLCJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3,4-dihydro-3-methyl-1H-benzopyran-5,8-dione 在 [FeL1(THF)(OTf)₂] 、 氧气 作用下， 60.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 以5%的产率得到1,1'-oxybis(3-methyl-3,4-dihydro-1H-isochromene-5,8-dione)
  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
• 作为产物：
  描述：

  3,4-dihydro-5,8-dimethoxy-3-methyl-1H-benzopyran 在 silver(II) oxide 、 硝酸 作用下， 以 1,4-二氧六环 为溶剂， 以99%的产率得到3,4-dihydro-3-methyl-1H-benzopyran-5,8-dione
  参考文献：
  名称：

  Retamal, J. I.; Ruiz, V. M.; Tapia, R. A., Synthetic Communications, 1982, vol. 12, # 4, p. 279 - 286

  摘要：

  DOI：

文献信息

• Retamal, J. I.; Ruiz, V. M.; Tapia, R. A., Synthetic Communications, 1982, vol. 12, # 4, p. 279 - 286
  作者：Retamal, J. I.、Ruiz, V. M.、Tapia, R. A.、Valderrama, J. A.、Vega, J. C.

  DOI：——

  日期：——
• Green, Ivan R.; Hugo, Victor I.; Oosthuisen, Francois J., South African Journal of Chemistry, 1994, vol. 48, # 1/2, p. 15 - 22
  作者：Green, Ivan R.、Hugo, Victor I.、Oosthuisen, Francois J.、Eeden, Nestor van、Giles, Robin G. F.

  DOI：——

  日期：——
• RETAMAL, J. I.;RUIZ, V. M.;TAPIA, R. A.;VALDERRAMA, J. A.;VEGA, J. C., SYNTH. COMMUN., 1982, 12, N 4, 279-285
  作者：RETAMAL, J. I.、RUIZ, V. M.、TAPIA, R. A.、VALDERRAMA, J. A.、VEGA, J. C.

  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.