3-benzenesulfinyl-N-benzo[1,3]dioxol-5-ylmethyl-N-tert-butylacrylamide | 207350-09-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 3-benzenesulfinyl-N-benzo[1,3]dioxol-5-ylmethyl-N-tert-butylacrylamide
• 英文别名: (Z)-3-(benzenesulfinyl)-N-(1,3-benzodioxol-5-ylmethyl)-N-tert-butylprop-2-enamide
• CAS: 207350-09-2
• 化学式: C₂₁H₂₃NO₄S
• 分子量: 385.484
• InChiKey: ONNGZSNFZVBIIU-QXMHVHEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  75
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-benzenesulfinyl-N-benzo[1,3]dioxol-5-ylmethyl-N-tert-butylacrylamide 在 三氟甲磺酸酐 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以15%的产率得到6-tert-Butyl-8-[1-phenylsulfanyl-meth-(Z)-ylidene]-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquinolin-7-one
  参考文献：
  名称：

  Additive and Vinylogous Pummerer Reactions of Amido Sulfoxides and Their Use in the Preparation of Nitrogen Containing Heterocycles

  摘要：

  The alpha-thiocarbocation generated from the Pummerer re action of N-methyl-N-phenyl-2-[2-(toluene-4-sulfinyl)phenyl]acetamide undergoes Friedel-Crafts reaction at the gamma-carbon with the tethered aromatic ring. Reductive removal of the phenylthio group from the resulting product using Raney nickel occurs in high yield, and the overall reaction represents a new method for the synthesis of a variety of 3-phenyl-substituted oxindoles. Treatment of the related N-benzyl-N-alkyl amido sulfoxide system with trifluoroacetic anhydride affords tetrahydroisoquinolone derivatives. The product distribution encountered coincides with the rotamer population of the starting amide. When the N-benzyl-N-methyl amide is used, only the normal Pummerer product is formed. In this case, the thionium ion is generated in the wrong conformation for pi-cyclization to occur. The corresponding N-tert-butyl amido system, however, exists in a geometric orientation which places the benzylic group in the crucial conformation necessary for pi-cyclization, and consequently, the reaction proceeds smoothly. Related cyclization reactions occur in good yield with the corresponding furanyl and cyclohexenyl N-tert-butyl amido sulfoxides. The additive Pummerer reaction of 3-phenylsulfinyl-N-benzyl-N-tert-butylacrylamide gave products derived from both 5- and 6-exo trig cyclizations. Intramolecular electrophilic aromatic substitution via six-membered ring closure ultimately afforded a dihydropyridone. The competitive process involving ipso attack of the aromatic ring on the thionium ion generates a spiro cyclohexadienyl cation that undergoes fragmentation of the adjacent a-bond. The resulting acyl iminium ion is converted to N-tert-butyl-2-phenyl-3-phenylsulfinylacrylamide upon aqueous workup. Only cyclizations leading to five-membered rings occur with the corresponding indolyl and alkenyl N-tert-butyl amido sulfoxides.

  DOI：

  10.1021/jo972093h
• 作为产物：
  描述：

  benzo[1,3]dioxol-5-ylmethyl-tert-butylamine 在 titanium(III) chloride 、 草酰氯 、 双氧水 、 N,N-二甲基甲酰胺 作用下， 以 甲醇 、 水 、 乙腈 、 苯 为溶剂， 反应 2.17h， 生成 3-benzenesulfinyl-N-benzo[1,3]dioxol-5-ylmethyl-N-tert-butylacrylamide
  参考文献：
  名称：

  Additive and Vinylogous Pummerer Reactions of Amido Sulfoxides and Their Use in the Preparation of Nitrogen Containing Heterocycles

  摘要：

  The alpha-thiocarbocation generated from the Pummerer re action of N-methyl-N-phenyl-2-[2-(toluene-4-sulfinyl)phenyl]acetamide undergoes Friedel-Crafts reaction at the gamma-carbon with the tethered aromatic ring. Reductive removal of the phenylthio group from the resulting product using Raney nickel occurs in high yield, and the overall reaction represents a new method for the synthesis of a variety of 3-phenyl-substituted oxindoles. Treatment of the related N-benzyl-N-alkyl amido sulfoxide system with trifluoroacetic anhydride affords tetrahydroisoquinolone derivatives. The product distribution encountered coincides with the rotamer population of the starting amide. When the N-benzyl-N-methyl amide is used, only the normal Pummerer product is formed. In this case, the thionium ion is generated in the wrong conformation for pi-cyclization to occur. The corresponding N-tert-butyl amido system, however, exists in a geometric orientation which places the benzylic group in the crucial conformation necessary for pi-cyclization, and consequently, the reaction proceeds smoothly. Related cyclization reactions occur in good yield with the corresponding furanyl and cyclohexenyl N-tert-butyl amido sulfoxides. The additive Pummerer reaction of 3-phenylsulfinyl-N-benzyl-N-tert-butylacrylamide gave products derived from both 5- and 6-exo trig cyclizations. Intramolecular electrophilic aromatic substitution via six-membered ring closure ultimately afforded a dihydropyridone. The competitive process involving ipso attack of the aromatic ring on the thionium ion generates a spiro cyclohexadienyl cation that undergoes fragmentation of the adjacent a-bond. The resulting acyl iminium ion is converted to N-tert-butyl-2-phenyl-3-phenylsulfinylacrylamide upon aqueous workup. Only cyclizations leading to five-membered rings occur with the corresponding indolyl and alkenyl N-tert-butyl amido sulfoxides.

  DOI：

  10.1021/jo972093h

文献信息

• Additive and Vinylogous Pummerer Reactions of Amido Sulfoxides and Their Use in the Preparation of Nitrogen Containing Heterocycles
  作者：Albert Padwa、Jeffrey T. Kuethe

  DOI：10.1021/jo972093h

  日期：1998.6.1

  The alpha-thiocarbocation generated from the Pummerer re action of N-methyl-N-phenyl-2-[2-(toluene-4-sulfinyl)phenyl]acetamide undergoes Friedel-Crafts reaction at the gamma-carbon with the tethered aromatic ring. Reductive removal of the phenylthio group from the resulting product using Raney nickel occurs in high yield, and the overall reaction represents a new method for the synthesis of a variety of 3-phenyl-substituted oxindoles. Treatment of the related N-benzyl-N-alkyl amido sulfoxide system with trifluoroacetic anhydride affords tetrahydroisoquinolone derivatives. The product distribution encountered coincides with the rotamer population of the starting amide. When the N-benzyl-N-methyl amide is used, only the normal Pummerer product is formed. In this case, the thionium ion is generated in the wrong conformation for pi-cyclization to occur. The corresponding N-tert-butyl amido system, however, exists in a geometric orientation which places the benzylic group in the crucial conformation necessary for pi-cyclization, and consequently, the reaction proceeds smoothly. Related cyclization reactions occur in good yield with the corresponding furanyl and cyclohexenyl N-tert-butyl amido sulfoxides. The additive Pummerer reaction of 3-phenylsulfinyl-N-benzyl-N-tert-butylacrylamide gave products derived from both 5- and 6-exo trig cyclizations. Intramolecular electrophilic aromatic substitution via six-membered ring closure ultimately afforded a dihydropyridone. The competitive process involving ipso attack of the aromatic ring on the thionium ion generates a spiro cyclohexadienyl cation that undergoes fragmentation of the adjacent a-bond. The resulting acyl iminium ion is converted to N-tert-butyl-2-phenyl-3-phenylsulfinylacrylamide upon aqueous workup. Only cyclizations leading to five-membered rings occur with the corresponding indolyl and alkenyl N-tert-butyl amido sulfoxides.