2,2-Dimethyl-3-(5-methyl-cyclopent-1-enyl)-propionaldehyde | 145124-50-1

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: 2,2-Dimethyl-3-(5-methyl-cyclopent-1-enyl)-propionaldehyde
• 英文别名: 2,2-Dimethyl-3-(5-methylcyclopenten-1-yl)propanal
• CAS: 145124-50-1
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: FYROTDVJDQBTEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-3-(5-methyl-cyclopent-1-enyl)-propionaldehyde 在 咪唑 、 正丁基锂 、 一氧化碳 作用下， 以 正庚烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 生成 9-(tert-Butyldimethylsiloxy)-2,10,10-trimethyltricyclo<6.3.0.0.^1,5>undec-7-en-6-one
  参考文献：
  名称：

  The Pauson-Khand reaction in triquinane synthesis: approaches to pentalenene, pentalenic acid, and silphinene

  摘要：

  Substituted pentynylcyclopentene precursors for the synthesis of pentalenene, pentalenic acid, and silphinene by intramolecular Pauson-Khand cycloaddition reaction have been prepared from 2-methylcyclopentanone via 5-methylcyclopentenyllithium. Conjugate addition of the latter to BHT methacrylate followed by methylation were the key steps in enyne synthesis. Reaction of 4,4-dimethyl-5-(5-methylcyclopentenyl)-1-pen e with Co2(CO)8 produces two diastereomeric triquinane enones in an overall yield of 51%, with the exo-9-methyl isomer predominating by ratio of 8:1. This material was converted into pentalenene in two steps. Pauson-Khand reaction of the TBDMS ether of 4,4-dimethyl-5-(5-methylcyclopentenyl)-1-pentyn-3-ol proceeds in 33% yield. Three of the four possible stereoisomeric products are formed, with two of them, making up ca. 80% of the product mixture, possessing the necessary exo-methyl stereochemistry at C-9 for further elaboration into pentalenic acid. A formal synthesis of the latter was completed by reduction of one of the enone isomers into a ketone which had previously been carried on to the natural product. Pd(0)-catalyzed coupling of 1-iodo-5-methylcyclopentene to 1-(trimethylsilyl)-1,4-pentadiyne and reduction over Lindlar's catalyst allowed efficient access to (Z)-1-(5-methylcyclopentenyl)-1-penten-4-yne, but the latter could not be induced to undergo Pauson-Khand cyclization, thus foiling a planned approach to silphinene.

  DOI：

  10.1021/jo00051a034
• 作为产物：
  描述：

  2-(2,2-Dimethyl-3-hydroxypropyl)-3-methylcyclopentene 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 2,2-Dimethyl-3-(5-methyl-cyclopent-1-enyl)-propionaldehyde
  参考文献：
  名称：

  The Pauson-Khand reaction in triquinane synthesis: approaches to pentalenene, pentalenic acid, and silphinene

  摘要：

  Substituted pentynylcyclopentene precursors for the synthesis of pentalenene, pentalenic acid, and silphinene by intramolecular Pauson-Khand cycloaddition reaction have been prepared from 2-methylcyclopentanone via 5-methylcyclopentenyllithium. Conjugate addition of the latter to BHT methacrylate followed by methylation were the key steps in enyne synthesis. Reaction of 4,4-dimethyl-5-(5-methylcyclopentenyl)-1-pen e with Co2(CO)8 produces two diastereomeric triquinane enones in an overall yield of 51%, with the exo-9-methyl isomer predominating by ratio of 8:1. This material was converted into pentalenene in two steps. Pauson-Khand reaction of the TBDMS ether of 4,4-dimethyl-5-(5-methylcyclopentenyl)-1-pentyn-3-ol proceeds in 33% yield. Three of the four possible stereoisomeric products are formed, with two of them, making up ca. 80% of the product mixture, possessing the necessary exo-methyl stereochemistry at C-9 for further elaboration into pentalenic acid. A formal synthesis of the latter was completed by reduction of one of the enone isomers into a ketone which had previously been carried on to the natural product. Pd(0)-catalyzed coupling of 1-iodo-5-methylcyclopentene to 1-(trimethylsilyl)-1,4-pentadiyne and reduction over Lindlar's catalyst allowed efficient access to (Z)-1-(5-methylcyclopentenyl)-1-penten-4-yne, but the latter could not be induced to undergo Pauson-Khand cyclization, thus foiling a planned approach to silphinene.

  DOI：

  10.1021/jo00051a034