5α-hydroxy-2-oxo-p-menth-6(1)-ene

• 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: 5α-hydroxy-2-oxo-p-menth-6(1)-ene
• 英文别名: 5α-hydroxy-8,9-dihydrocarvone；(+)-(4R,5R)-4-hydroxy-5-isopropyl-2-methylcyclohex-2-enone；trans-5-hydroxy-p-menth-6-en-2-one；5-hydroxy-2-oxo-p-menth-6(1)-ene；trans-p-menth-1-en-3-ol-6-one；trans-5-Hydroxy-p-menth-1(6)-en-2-one；(4S,5S)-4-hydroxy-2-methyl-5-propan-2-ylcyclohex-2-en-1-one
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: ZFUJCNJIGDBFEP-WCBMZHEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5α-hydroxy-2-oxo-p-menth-6(1)-ene 在 4-二甲氨基吡啶 、 氢氟酸 、 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 48.5h， 生成 (1S,2S,4aR,8aS)-2-isopropyl-4a-methyl-4,7-dioxo-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl benzoate
  参考文献：
  名称：

  （+）-Sarcophytin，（+）-Chatancin，（-）-3-Oxochatancin和（-）-Pavidolide B的总合成：一种不同的方法。

  摘要：

  已经开发出一种简洁且不同的方法来合成四种西c二萜类化合物，即（+）-石蒜素，（+）-查塔霉素，（-）-3-氧代查他霉素和（-）-pavidolide B）。导致（-）-异石藻素的结构修订。该策略的关键步骤包括双重Mukaiyama Michael加法/消除法，Helquist法制环法，两个受底物控制的面部选择性水合作用以及频哪醇重排。所描述的合成不仅以有效的方式获得了这些天然产物，而且还提供了对两个不同骨架之间生物合成关系的了解。

  DOI：

  10.1002/anie.201900782
• 作为产物：
  描述：

  右旋香芹酮 在 Wilkinson's catalyst 、 copper aluminate 、 potassium tert-butylate 、 氢气 作用下， 以 乙醇 、 甲苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 生成 5α-hydroxy-2-oxo-p-menth-6(1)-ene
  参考文献：
  名称：

  （-）-Pavidolide B的不对称总合成是通过巯基-自由基介导的[3 + 2]环化反应。

  摘要：

  详细描述了生物活性海洋天然产物（-）-pavidolide B不对称全合成的有效策略的开发。描绘了导致关键的噻吩基-自由基介导的[3 + 2]环化反应的过程和绕行过程，该反应一步一步构建了具有四个连续立体中心的中心C环。随后，通过闭环易位反应，然后进行Rh（III）催化的异构化反应，构建了七元D环。该策略能够以最长的10步线性序列进行（-）-pavidolide B的全合成。

  DOI：

  10.1021/acs.joc.9b02230

文献信息

• Total Synthesis of (+)‐Sarcophytin
  作者：Leonardo J. Nannini、Suren J. Nemat、Erick M. Carreira

  DOI：10.1002/anie.201711372

  日期：2018.1.15

  A total synthesis of the cembranoid (+)‐sarcophytin is presented, featuring a Diels–Alder cycloaddition of an enone as the dienophile with an ester‐derived dienoate. The study highlights a peculiar geometric preference for the Z dienoate to furnish the cycloadduct. The endgame involves a reaction cascade, including lactone opening, alcohol oxidation, and ketone epimerization to complete an efficient

  提出了一种共生的cembranoid（+）-sarcophytin合成方法，其特征是将Diones-Alder环加成二烯酮作为烯二酮与酯衍生的二烯酸酯。这项研究突出了Z 烯醛酸的独特几何构型，以提供环加合物。最终阶段涉及反应级联反应，包括内酯开放，醇氧化和酮差向异构化，以完成有效的合成。合成的一个显着特征是对绝对构型的重新分配，从而纠正了先前报道的标称结构。
• Enantioselective Total Synthesis of (−)-Pavidolide B
  作者：Peng-Peng Zhang、Zhi-Ming Yan、Yuan-He Li、Jian-Xian Gong、Zhen Yang

  DOI：10.1021/jacs.7b07388

  日期：2017.10.11

  The enantioselective synthesis of (-)-pavidolide B (1) was achieved in a linear sequence of 10 steps. The key steps are (a) an enantioselective organocatalytic cyclopropanation; (b) a radical-based cascade annulation for the regio- and diastereo-selective synthesis of the highly functionalized lactone 3 bearing the characteristic tricyclic core and seven contiguous stereocenters;

  (-)-pavidolide B (1) 的对映选择性合成是以 10 步的线性序列实现的。关键步骤是 (a) 对映选择性有机催化环丙烷化反应；(b) 基于自由基的级联环化，用于高功能化内酯 3 的区域和非对映选择性合成，其具有特征三环核心和七个连续的立体中心；
• Total Synthesis of (−)-Pavidolide B: A Ring Contraction Strategy
  作者：Peirong Rao、Jialei Hu、Jun Xuan、Hanfeng Ding

  DOI：10.1021/acs.joc.9b01308

  日期：2019.7.19

  A ring contraction approach for the total synthesis of (−)-pavidolide B was developed, which assembles this polycyclic natural product within 13 steps from known chiral alcohol 11. The key features of the strategy include (a) a double Mukaiyama–Michael addition/elimination, (b) a ring-closing metathesis, (c) a Wolff rearrangement, and (d) a late-stage regioselective Schenck ene reaction.

  开发了一种用于全合成（-）-pavidolide B的环收缩方法，该方法在已知手性醇11的13个步骤内组装了该多环天然产物。该策略的主要特征包括（a）两次开山-迈克尔加成/消除反应；（b）闭环复分解反应；（c）Wolff重排；以及（d）后期区域选择性申克烯反应。
• Comparative analysis of three Australian finger lime (Citrus australasica) cultivars: Identification of unique citrus chemotypes and new volatile molecules
  作者：Estelle Delort、Alain Jaquier、Erik Decorzant、Christian Chapuis、Alessandro Casilli、Eric Frérot

  DOI：10.1016/j.phytochem.2014.10.023

  日期：2015.1

  The volatile constituents of the peel of three cultivars of Australian finger lime (Citrus australasica) were investigated: Alstonville, Judy's Everbearing and Durham's Emerald. Both qualitative and quantitative GC-MS analyses were performed on their peel solvent extract. The results showed that the unique phenotypes of finger lime are also correlated to unique molecular compositions. Each cultivar revealed a different chemotype: limonene/sabinene for cv. Alstonville, limonene/citronellal/isomenthone for cv. Judy's Everbearing, and limonene/citronellal/ citronellol for cv. Durham's Emerald. To the best of our knowledge, these chemotypes have never been reported in any other citrus species. Furthermore, the amounts of some volatile constituents (gamma-terpinene, alpha-pinene, beta-pinene, citral), which are generally the major constituents besides limonene in lime species, were surprisingly low in the three cultivars. Comparative GC-MS analysis also showed that some volatile molecules tended to be specific to one cultivar and could therefore be considered as markers. Moreover six molecules were reported for the first time in a citrus extract and confirmed by synthesis. Heart-cutting enantioselective two-dimensional GC-MS was performed to determine the enantiomeric distribution of the major chiral constituents. The combined data on three finger lime cultivars gives evidence of their divergence from other citrus species. (C) 2014 Elsevier Ltd. All rights reserved.