2-(p-tolylsulfonyl)-5,5-dimethylcyclopentenone | 153257-13-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(p-tolylsulfonyl)-5,5-dimethylcyclopentenone
• 英文别名: 5,5-Dimethyl-2-tosyl-cyclopent-2-en-1-one；5,5-dimethyl-2-(4-methylphenyl)sulfonylcyclopent-2-en-1-one
• CAS: 153257-13-7
• 化学式: C₁₄H₁₆O₃S
• 分子量: 264.345
• InChiKey: FXVRCMZJAMINRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(p-tolylsulfonyl)-5,5-dimethylcyclopentenone 在 rhodium(II) acetate dimer 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 spiro[8-hydroxy-1,4,4,8-tetramethyl-2α-(p-tolylsulfonyl)-10-oxatricyclo[5.2.1.0^2,6]deca-3,8-dione-9,1'-cyclopropane]
  参考文献：
  名称：

  An Approach toward the Illudin Family of Sesquiterpenes Using the Tandem Cyclization−Cycloaddition Reaction of Rhodium Carbenoids

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane with 5,5-dimethylcyclopentenone afforded the product of a 1,3-dipolar cycloaddition in high yield. The reaction involves formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent 1,3-dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. Treatment of the cycloadduct with p-toluene-sulfonic acid results in loss of water followed by a subsequent acid-catalyzed cyclopropyl ketone rearrangement to give dihydrobenzofuran 21. The product distribution derived from the SmI2-induced reduction of the dipolar cycloadduct was found to depend on the reaction conditions. Under kinetic conditions, the reduction resulted in opening of the cyclopropyl ring adjacent to the carbonyl group. However, under thermodynamic conditions, cleavage of the oxy bridge corresponded to the major pathway. The cycloaddition-reduction protocol provides a rapid assembly of the basic core unit of ptaquilosin having most of the functionality in place. Generation of a carbanion adjacent to the oxy bridge leads to opening of the oxabicyclic ring system in a highly regioselective manner. A short synthesis of (+/-)-illudin M and the closely related isodehydroilludin M is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide.

  DOI：

  10.1021/jo961574i
• 作为产物：
  描述：

  (trimethylacetyl)(phenyl{[(trifluoromethyl)sulfonyl]oxy}iodo)acetylene 、 sodium 4-methylbenzenesulfinate 以 二氯甲烷 为溶剂， 反应 0.5h， 以73%的产率得到2-(p-tolylsulfonyl)-5,5-dimethylcyclopentenone
  参考文献：
  名称：

  An Approach toward the Illudin Family of Sesquiterpenes Using the Tandem Cyclization−Cycloaddition Reaction of Rhodium Carbenoids

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane with 5,5-dimethylcyclopentenone afforded the product of a 1,3-dipolar cycloaddition in high yield. The reaction involves formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent 1,3-dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. Treatment of the cycloadduct with p-toluene-sulfonic acid results in loss of water followed by a subsequent acid-catalyzed cyclopropyl ketone rearrangement to give dihydrobenzofuran 21. The product distribution derived from the SmI2-induced reduction of the dipolar cycloadduct was found to depend on the reaction conditions. Under kinetic conditions, the reduction resulted in opening of the cyclopropyl ring adjacent to the carbonyl group. However, under thermodynamic conditions, cleavage of the oxy bridge corresponded to the major pathway. The cycloaddition-reduction protocol provides a rapid assembly of the basic core unit of ptaquilosin having most of the functionality in place. Generation of a carbanion adjacent to the oxy bridge leads to opening of the oxabicyclic ring system in a highly regioselective manner. A short synthesis of (+/-)-illudin M and the closely related isodehydroilludin M is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide.

  DOI：

  10.1021/jo961574i

文献信息

• Williamson, Bobby L.; Tykwinski, Rik R.; Stang, Peter J., Journal of the American Chemical Society, 1994, vol. 116, # 1, p. 93 - 98
  作者：Williamson, Bobby L.、Tykwinski, Rik R.、Stang, Peter J.

  DOI：——

  日期：——
• An Approach toward the Illudin Family of Sesquiterpenes Using the Tandem Cyclization−Cycloaddition Reaction of Rhodium Carbenoids
  作者：Albert Padwa、Erin A. Curtis、Vincent P. Sandanayaka

  DOI：10.1021/jo961574i

  日期：1997.3.1

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane with 5,5-dimethylcyclopentenone afforded the product of a 1,3-dipolar cycloaddition in high yield. The reaction involves formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent 1,3-dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. Treatment of the cycloadduct with p-toluene-sulfonic acid results in loss of water followed by a subsequent acid-catalyzed cyclopropyl ketone rearrangement to give dihydrobenzofuran 21. The product distribution derived from the SmI2-induced reduction of the dipolar cycloadduct was found to depend on the reaction conditions. Under kinetic conditions, the reduction resulted in opening of the cyclopropyl ring adjacent to the carbonyl group. However, under thermodynamic conditions, cleavage of the oxy bridge corresponded to the major pathway. The cycloaddition-reduction protocol provides a rapid assembly of the basic core unit of ptaquilosin having most of the functionality in place. Generation of a carbanion adjacent to the oxy bridge leads to opening of the oxabicyclic ring system in a highly regioselective manner. A short synthesis of (+/-)-illudin M and the closely related isodehydroilludin M is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide.