Toluene-4-sulfonic acid 5-hydroxy-2,2-dimethyl-4-oxo-chroman-7-yl ester | 676529-26-3

• 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: Toluene-4-sulfonic acid 5-hydroxy-2,2-dimethyl-4-oxo-chroman-7-yl ester
• 英文别名: (5-hydroxy-2,2-dimethyl-4-oxo-3H-chromen-7-yl) 4-methylbenzenesulfonate
• CAS: 676529-26-3
• 化学式: C₁₈H₁₈O₆S
• 分子量: 362.403
• InChiKey: IFRPGDMGSNZHSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  98.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Toluene-4-sulfonic acid 5-hydroxy-2,2-dimethyl-4-oxo-chroman-7-yl ester 在 盐酸 、 palladium diacetate 、 氢氧化钾 、 甲酸 、 sodium acetate 、 potassium carbonate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 锌 作用下， 以 乙醇 、 丙酮 、 苯 为溶剂， 反应 49.0h， 生成 黄木亭
  参考文献：
  名称：

  Atom Economy. Palladium-Catalyzed Formation of Coumarins by Addition of Phenols and Alkynoates via a Net C−H Insertion

  摘要：

  A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.

  DOI：

  10.1021/ja0286573
• 作为产物：
  描述：

  3,3-二甲基丙烯酸 在 potassium carbonate 、 zinc(II) chloride 、 三氯氧磷 作用下， 以 丙酮 为溶剂， 反应 23.0h， 生成 Toluene-4-sulfonic acid 5-hydroxy-2,2-dimethyl-4-oxo-chroman-7-yl ester
  参考文献：
  名称：

  Atom Economy. Palladium-Catalyzed Formation of Coumarins by Addition of Phenols and Alkynoates via a Net C−H Insertion

  摘要：

  A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.

  DOI：

  10.1021/ja0286573

文献信息

• Atom Economy. Palladium-Catalyzed Formation of Coumarins by Addition of Phenols and Alkynoates via a Net C−H Insertion
  作者：Barry M. Trost、F. Dean Toste、Kevin Greenman

  DOI：10.1021/ja0286573

  日期：2003.4.1

  A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.