2-<(3'-diazoacetonyl)thio>pyridine | 562828-42-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-<(3'-diazoacetonyl)thio>pyridine
• 英文别名: 1-Diazo-3-(pyridin-2-ylsulfanyl) propan-2-one；1-diazo-3-pyridin-2-ylsulfanylpropan-2-one
• CAS: 562828-42-6
• 化学式: C₈H₇N₃OS
• 分子量: 193.229
• InChiKey: BUXKRDHNXUFBTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  57.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-<(3'-diazoacetonyl)thio>pyridine 、 富马酸二甲酯 在 rhodium(II) acetate dimer 作用下， 以 氯仿 为溶剂， 反应 0.5h， 以90%的产率得到(+/-)-(3aα,4α,5β,5aα)-4,5-dicarbomethoxy-2,3,3a,4,5,5a-hexahydro<1,3>thiazino<4,3,2-c,d>indolizin-3-one
  参考文献：
  名称：

  Cycloaddition reactions of pyridinium and related azomethine ylides

  摘要：

  The Rh(H)-catalyzed reaction of alpha-diazoacetophenone in the presence of 2-(methylthio)pyridine and dimethyl acetylenedicarboxylate gave 3-benzoyl-1,2-dicarbomethoxy-3,5-dihydro-5-(methylthio)-indolizine. The formation of the cycloadduct proceeds via a pyridinium ylide formed by attack of the nitrogen lone pair on the electrophilic keto carbenoid. A related cyclization occurred using 1-diazo-3-[(2-pyridyl)thio]-2-propanone. The Rh(II)-catalyzed reaction of 1-(3'-diazoacetonyl)-2-pyridone with DMAD was also found to give cycloadducts derived from an azomethine ylide. The initial reaction involves generation of the expected carbonyl ylide dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group. A subsequent proton exchange generates the thermodynamically more stable azomethine ylide which is trapped by DMAD. Azomethine ylide cycloadducts derived from keto carbenoid cyclization onto a thiobenzoxazole are also formed. When 1-diazo-3-[(2-benzoxazolyl)thio]-2-propanone was used, the initially formed cycloadduct underwent a subsequent 1,3-sigmatropic thio shift. An analogous cyclization occurred using 2-(4-diazo-3-oxobutyl)benzoxazole. In addition to undergoing dipolar cycloaddition, the highly stabilized dipole formed from this benzoxazole loses a proton to produce a cyclic ketene N,O-acetal. This compound reacts further with DMAD to eventually produce a novel phenolic lactam whose structure was established by an X-ray crystal structure analysis.

  DOI：

  10.1021/jo00057a029
• 作为产物：
  描述：

  1-bromo-3-diazopropan-2-one 、 2-巯基吡啶 在 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以83%的产率得到2-<(3'-diazoacetonyl)thio>pyridine
  参考文献：
  名称：

  Cycloaddition reactions of pyridinium and related azomethine ylides

  摘要：

  The Rh(H)-catalyzed reaction of alpha-diazoacetophenone in the presence of 2-(methylthio)pyridine and dimethyl acetylenedicarboxylate gave 3-benzoyl-1,2-dicarbomethoxy-3,5-dihydro-5-(methylthio)-indolizine. The formation of the cycloadduct proceeds via a pyridinium ylide formed by attack of the nitrogen lone pair on the electrophilic keto carbenoid. A related cyclization occurred using 1-diazo-3-[(2-pyridyl)thio]-2-propanone. The Rh(II)-catalyzed reaction of 1-(3'-diazoacetonyl)-2-pyridone with DMAD was also found to give cycloadducts derived from an azomethine ylide. The initial reaction involves generation of the expected carbonyl ylide dipole by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group. A subsequent proton exchange generates the thermodynamically more stable azomethine ylide which is trapped by DMAD. Azomethine ylide cycloadducts derived from keto carbenoid cyclization onto a thiobenzoxazole are also formed. When 1-diazo-3-[(2-benzoxazolyl)thio]-2-propanone was used, the initially formed cycloadduct underwent a subsequent 1,3-sigmatropic thio shift. An analogous cyclization occurred using 2-(4-diazo-3-oxobutyl)benzoxazole. In addition to undergoing dipolar cycloaddition, the highly stabilized dipole formed from this benzoxazole loses a proton to produce a cyclic ketene N,O-acetal. This compound reacts further with DMAD to eventually produce a novel phenolic lactam whose structure was established by an X-ray crystal structure analysis.

  DOI：

  10.1021/jo00057a029

文献信息

• Padwa Albert, Austin David J., Precedo Laura, Zhi Lin, J. Org. Chem., 58 (1993) N 5, S 1144-1150
  作者：Padwa Albert, Austin David J., Precedo Laura, Zhi Lin

  DOI：——

  日期：——