(1R,2R)-tochuinyl acetate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,2R)-tochuinyl acetate
• 英文别名: [(1R,2R)-1,2-dimethyl-2-(4-methylphenyl)cyclopentyl]methyl acetate
• 化学式: C₁₇H₂₄O₂
• 分子量: 260.376
• InChiKey: ZHOBFAUFESISCM-DLBZAZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-甲基苯硫酚 在 吡啶 、 水 、 二氯乙基铝 、 镍 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 32.67h， 生成 (1R,2R)-tochuinyl acetate
  参考文献：
  名称：

  Synthesis of thiochromans by means of a (4++2) polar cycloaddition of m-tolylthiomethyl chloride with substituted alkenes: A simple synthesis of (.+-.)-cuparene and related sesquiterpenoids.

  摘要：

  (±)-Cuparene、(±)-α-cuparenone和(±)-tochuinyl acetate是通过使用Lewis酸介导的[4+2]极性环加成反应，以取代的环戊烯为关键步骤，从m-tolylthiomethyl chloride合成的。

  DOI：

  10.1248/cpb.38.1233

文献信息

• Enantioselective synthesis of natural (−)-tochuinyl acetate, (−)-dihydrotochuinyl acetate and (+)-β-cuparenone using both enantiomers of the same building block
  作者：Samir Acherar、Gérard Audran、Fabrice Cecchin、Honoré Monti

  DOI：10.1016/j.tet.2004.05.037

  日期：2004.7

  The first enantioselective synthesis of tochuinyl acetate and dihydrotochuinyl acetate, two natural marine products isolated from Tochuina tetraquetra and Gersemia rubiformis, has been achieved starting from an enantiopure building block. The key feature of the present synthesis is complete control of two vicinal quaternary stereogenic centers present in the natural products and elucidation of their

  从对映体纯净的结构单元开始，实现了乙酸甲苯酯和乙酸二氢甲苯酯的首次对映体选择性合成，这两种天然水产品是从四叶草（Tochuina tetraquetra）和红叶Gersemia分离得到的。本合成的关键特征是完全控制天然产物中存在的两个邻近的季生立体中心，并阐明了它们的绝对立体化学，这在以前是未知的。此外，从相同构件的对映异构体开始，所应用的方法为天然（R）-（+）-β-cuparenone提供了一种新方法。
• Stereoselective total synthesis of (±)-tochuinyl acetate and (±)-dihydrotochuinyl acetates
  作者：A. Srikrishna、T.Jagadeeswar Reddy

  DOI：10.1016/s0040-4020(98)00436-0

  日期：1998.7

  Details of the first total synthesis of the marine natural product dihydrotochuinyl acetate is described. Cyclopentenone annulation of p-methylacetophenone via a Claisen rearrangement-Wacker oxidation based sequence generated the cyclopentenone 3, a known precursor for the sesquiterpenes cuparene, laurene, α-cuparenone and β-cuparenones. Conversion of the ketone moiety into a carboxylate followed by

  描述了海洋天然产物乙酸二氢甲苯酯的第一全合成的细节。通过基于克莱森重排-Wacker氧化的序列对对甲基苯乙酮进行环戊烯酮环化，生成了环戊烯酮3，它是倍半萜烯铜烯，月桂烯，α-cuparenone和β-cuparenones的已知前体。酮部分转化为羧酸酯，随后进行立体选择性烷基化和还原，将环戊烯酮3转化为伯醇19。醇19的桦木还原，然后进行乙酰化，得到乙酸（±）-二氢甲苯基乙酸酯，而对乙酰基19进行直接乙酰化，得到乙酸（±）-二氢甲苯基乙酸酯。
• Rhodium-mediated cyclopentane construction can compete with .beta.-hydride elimination: synthesis of (.+-.)-tochuinyl acetate
  作者：Douglass F. Taber、Michael J. Hennessy、James P. Louey

  DOI：10.1021/jo00028a011

  日期：1992.1

  Rhodium(II) carboxylate catalyzed C-H insertion to form a cyclopentane is shown to compete effectively with beta-hydride elimination, except when the beta-hydrogen is ternary. Cyclization of diazo ester 27 gives 28, which is converted in three steps to (+/-)-tochuinyl acetate 25. Both the cyclization to form 28 and the alkylation of 28 proceed with remarkable diastereoselectivity.
• Stereoselective total syntheses of (±)-1,14-herbertenediol and (±)-tochuinyl acetate and facile total syntheses of (±)-α-herbertenol, (±)-β-herbertenol and (±)-1,4-cuparenediol
  作者：Tapas Paul、Ashutosh Pal、Pranab Dutta Gupta、Debabrata Mukherjee

  DOI：10.1016/s0040-4039(02)02674-6

  日期：2003.1

  Stereoselective total syntheses of (+/-)-1,14-herbertenediol (7) and (+/-)-tochuinyl acetate (10) and facile total syntheses of (+/-)-a=alpha-herbertenol (2), (+/-)-beta-herbertenol (3) and (+/-)-1,4-cuparenediol (8) have been successfully accomplished involving intramolecular cyclisation of 3-aryl-3-methyl-6-bromohexanoates and in situ methylation of the resulting cyclopentanecarboxylates as the key reactions. (C) 2003 Elsevier Science Ltd. All rights reserved.