Methyl 2,3-dihydro-2-hydroxy-α,α-dimethyl-1H-indene-2-acetate

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: Methyl 2,3-dihydro-2-hydroxy-α,α-dimethyl-1H-indene-2-acetate
• 英文别名: Methyl 2-(2-hydroxy-1,3-dihydroinden-2-yl)-2-methylpropanoate
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: FFCNGARYCODGQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 2,3-dihydro-2-hydroxy-α,α-dimethyl-1H-indene-2-acetate 在 吡啶 、 三氯氧磷 作用下， 反应 2.0h， 以83%的产率得到Methyl α,α-dimethyl-1H-indene-2-acetate
  参考文献：
  名称：

  A Ring Expansion Procedure Based on the Tandem Dealkoxycarbonylation-Michael Addition Reaction

  摘要：

  A three-step ring expansion procedure has been developed to convert methyl alpha,alpha-dialkyl-1-cyclopenteneacetates to highly functionalized cyclohexaneacetic esters. The procedure involves (1) ozonolytic double bond cleavage, (2) chemoselective Wittig olefination of the aldehyde carbonyl of the resulting keto aldehyde, and (3) tandem dealkoxycarbonylation-Michael addition to close the ring. The transformation proceeds best when the a-carbon of the starting acetate is quaternary, and thus, the method is unique in yielding hindered 2,2-dialkyl-3-oxocyclohexaneacetic esters. The reaction sequence is easily performed, and overall yields of 40-50% are readily achieved. The synthetic and mechanistic details of this process as well as optimization studies are presented. An analogous five-membered cyclization process was also investigated. Tandem dealkoxycarbonylation-Michael addition of 1-ethyl methyl (E)-7,7-dimethyl-6-oxo-2-octenedioate was found to afford a 24% isolated yield of ethyl 2,2-dimethyl-3-oxocyclopentaneacetate by a disfavored 5-[enolendo]-exo-trig process.

  DOI：

  10.1021/jo00114a024
• 作为产物：
  描述：

  异丁酸甲酯 、 2-茚酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 Methyl 2,3-dihydro-2-hydroxy-α,α-dimethyl-1H-indene-2-acetate
  参考文献：
  名称：

  A Ring Expansion Procedure Based on the Tandem Dealkoxycarbonylation-Michael Addition Reaction

  摘要：

  A three-step ring expansion procedure has been developed to convert methyl alpha,alpha-dialkyl-1-cyclopenteneacetates to highly functionalized cyclohexaneacetic esters. The procedure involves (1) ozonolytic double bond cleavage, (2) chemoselective Wittig olefination of the aldehyde carbonyl of the resulting keto aldehyde, and (3) tandem dealkoxycarbonylation-Michael addition to close the ring. The transformation proceeds best when the a-carbon of the starting acetate is quaternary, and thus, the method is unique in yielding hindered 2,2-dialkyl-3-oxocyclohexaneacetic esters. The reaction sequence is easily performed, and overall yields of 40-50% are readily achieved. The synthetic and mechanistic details of this process as well as optimization studies are presented. An analogous five-membered cyclization process was also investigated. Tandem dealkoxycarbonylation-Michael addition of 1-ethyl methyl (E)-7,7-dimethyl-6-oxo-2-octenedioate was found to afford a 24% isolated yield of ethyl 2,2-dimethyl-3-oxocyclopentaneacetate by a disfavored 5-[enolendo]-exo-trig process.

  DOI：

  10.1021/jo00114a024

文献信息

• A Ring Expansion Procedure Based on the Tandem Dealkoxycarbonylation-Michael Addition Reaction
  作者：Richard A. Bunce、Curtis L. III Schilling

  DOI：10.1021/jo00114a024

  日期：1995.5

  A three-step ring expansion procedure has been developed to convert methyl alpha,alpha-dialkyl-1-cyclopenteneacetates to highly functionalized cyclohexaneacetic esters. The procedure involves (1) ozonolytic double bond cleavage, (2) chemoselective Wittig olefination of the aldehyde carbonyl of the resulting keto aldehyde, and (3) tandem dealkoxycarbonylation-Michael addition to close the ring. The transformation proceeds best when the a-carbon of the starting acetate is quaternary, and thus, the method is unique in yielding hindered 2,2-dialkyl-3-oxocyclohexaneacetic esters. The reaction sequence is easily performed, and overall yields of 40-50% are readily achieved. The synthetic and mechanistic details of this process as well as optimization studies are presented. An analogous five-membered cyclization process was also investigated. Tandem dealkoxycarbonylation-Michael addition of 1-ethyl methyl (E)-7,7-dimethyl-6-oxo-2-octenedioate was found to afford a 24% isolated yield of ethyl 2,2-dimethyl-3-oxocyclopentaneacetate by a disfavored 5-[enolendo]-exo-trig process.