(4RS,9aSR)-1,4,9a-Trimethyl-1-(2-methyl-3-oxo-3H-inden-1-yl)-1,9a-dihydro-2,3-dithiafluoren-9-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (4RS,9aSR)-1,4,9a-Trimethyl-1-(2-methyl-3-oxo-3H-inden-1-yl)-1,9a-dihydro-2,3-dithiafluoren-9-one
• 英文别名: (1S,9aR)-1,4,9a-trimethyl-1-(2-methyl-3-oxoinden-1-yl)indeno[1,2-d]dithiin-9-one
• 化学式: C₂₄H₂₀O₂S₂
• 分子量: 404.554
• InChiKey: RSVAWONNMBFHPH-RPWUZVMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  84.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  硫化丙烯 、 2-Diazo-1-(2-prop-1-ynylphenyl)propan-1-one 在 rhodium(II) acetate dimer 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以97%的产率得到(4RS,9aSR)-1,4,9a-Trimethyl-1-(2-methyl-3-oxo-3H-inden-1-yl)-1,9a-dihydro-2,3-dithiafluoren-9-one
  参考文献：
  名称：

  A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones

  摘要：

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.

  DOI：

  10.1021/jo00106a014

文献信息

• A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M. David Weingarten

  DOI：10.1021/jo00106a014

  日期：1995.1

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.