2,6-Di-tert-butyl-4-methylphenyl 2,2-dimethyl-3-(5-methylcyclopentenyl)propanoate | 115482-78-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 2,6-Di-tert-butyl-4-methylphenyl 2,2-dimethyl-3-(5-methylcyclopentenyl)propanoate
• 英文别名: (2,6-ditert-butyl-4-methylphenyl) 2,2-dimethyl-3-(5-methylcyclopenten-1-yl)propanoate
• CAS: 115482-78-5
• 化学式: C₂₆H₄₀O₂
• 分子量: 384.602
• InChiKey: CQMIYTQNPVBGHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,6-Di-tert-butyl-4-methylphenyl 2,2-dimethyl-3-(5-methylcyclopentenyl)propanoate 在 咪唑 、 正丁基锂 、 草酰氯 、 一氧化碳 、 氨 、 sodium 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醚 、 乙醇 、 正庚烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 41.08h， 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：

  2,6-二叔丁基-4-甲基苯酚 在 正丁基锂 作用下， 反应 0.25h， 生成 2,6-Di-tert-butyl-4-methylphenyl 2,2-dimethyl-3-(5-methylcyclopentenyl)propanoate
  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

文献信息

• Diastereofacialselectivity in intramolecular Pauson-Khand cycloaddition. Highly stereoselective synthesis of pentalenene
  作者：Neil E. Schore、Elizabeth G. Rowley

  DOI：10.1021/ja00223a069

  日期：1988.7

  Preparation de deux isomeres de triquinanes dont la structure est celle d'un cyclopenta [h] pentalene a partir de methyl-5 cyclopentene-1yl lithium et de methyl-2 acrylate d'aryle [de BHA ou BHT]. Cette synthese permet, a partir d'une methode deja utilisee, de parvenir au pentalenene

  制备 de deux isomeres de triquinanes dont la structure est celle d'un cyclopenta [h] pentalene a partir demethyl-5 cyclopentene-1yl 锂和 demethyl-2 丙烯酸酯 d'aryle [de BHA ou BHT]。Cette synthese permet, a partir d'une methode deja utilisee, de parvenir au pentalenene
• SCHORE, NEIL E.;ROWLEY, ELIZABETH G., J. AMER. CHEM. SOC., 110,(1988) N 15, 5224-5225
  作者：SCHORE, NEIL E.、ROWLEY, ELIZABETH G.

  DOI：——

  日期：——