11,12-Dihydroxyabieta-8,11,13-trien-6-one | 81446-02-8

• 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: 11,12-Dihydroxyabieta-8,11,13-trien-6-one
• 英文别名: (+/-)-11,12-Dihydroxyabieta-8,11,13-trien-6-on；(4bR,8aR)-3,4-dihydroxy-4b,8,8-trimethyl-2-propan-2-yl-6,7,8a,10-tetrahydro-5H-phenanthren-9-one
• CAS: 81446-02-8
• 化学式: C₂₀H₂₈O₃
• 分子量: 316.441
• InChiKey: HMSMGZICKPDMDJ-QUCCMNQESA-N

物化性质

• 沸点：
  460.6±45.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  23.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  57.53
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  11,12-Dihydroxyabieta-8,11,13-trien-6-one 在 氧气 、 silica gel 作用下， 生成 6,9-dioxo-5-hydroxy-7-(1-methylethyl)-1,2,3,4,4aβ,6,10,10aα-octahydro-1,1,4a-trimethylphenanthrene
  参考文献：
  名称：

  A concise biomimetic total synthesis of (±)-taxodione via a BF₃·MeNO₂promoted cationic cascade annulation

  摘要：

  描述了抗肿瘤剂(±)-紫杉二酮1的高度收敛的七步全合成，其利用BF3·MeNO2络合物介导的阳离子级联环化。

  DOI：

  10.1039/c39920000502
• 作为产物：
  描述：

  1-chloromethyl-3,4-dimethoxy-5-(1-methylethyl)benzene 在 盐酸 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 氧气 、 三溴化硼 、 boron trifluoride nitrometane adduct 、 tin(ll) chloride 、 lithium diisopropyl amide 作用下， 以 硝基甲烷 、 二氯甲烷 为溶剂， 反应 0.08h， 生成 11,12-Dihydroxyabieta-8,11,13-trien-6-one
  参考文献：
  名称：

  A concise biomimetic total synthesis of (±)-taxodione via a BF₃·MeNO₂promoted cationic cascade annulation

  摘要：

  描述了抗肿瘤剂(±)-紫杉二酮1的高度收敛的七步全合成，其利用BF3·MeNO2络合物介导的阳离子级联环化。

  DOI：

  10.1039/c39920000502

文献信息

• Polyene cascade cyclizations mediated by BF3·CH3NO2. an unusually efficient method for the direct, stereospecific synthesis of polycyclic intermediates via cationic initiation at non-functionalized 3° alkenes. An application to the total synthesis of (±)-taxodione.
  作者：Scott R. Harring、Tom Livinghouse

  DOI：10.1016/s0040-4020(01)85502-2

  日期：——

  catalyzed” polyene cyclizations that proceed with excellent levels of regio- and stereocontrol. A direct comparison of this new method for effecting cationic polyannulations to several modern as well as classical procedures has conclusively defined the preparative advantages of the BF3·CH3NO2 medium. The utilization of these new conditions for cationic polycyclization in a concise total synthesis of the antineoplastic

  BF 3气体在硝基甲烷中的便捷储备溶液已显示出可促进“ H +催化”多烯环化反应，并以极佳的区域和立体控制水平进行。甲直接这种新方法的用于实现阳离子polyannulations若干现代以及经典程序相比，已经结论性地确定的BF的制备优点3 ·CH 3 NO 2平台。描述了这些新条件用于阳离子多环化的简明全合成抗肿瘤药（±）-紫杉二酮。
• Programmed Polyene Cyclization Enabled by Chromophore Disruption
  作者：Megan M. Solans、Vitalii S. Basistyi、James A. Law、Noah M. Bartfield、James H. Frederich

  DOI：10.1021/jacs.2c02144

  日期：2022.4.13

  A new polyene cyclization strategy exploiting β-ionyl derivatives was developed. Photoinduced deconjugation of the extended π-system within these chromophores unveils a contrathermodynamic polyene that engages in a Heck bicyclization to afford [4.4.1]-propellanes. This cascade improves upon the limited regioselectivity achieved using existing biomimetic tactics and tolerates both electron-rich and

  开发了一种利用 β-离子酰基衍生物的新多烯环化策略。这些发色团内扩展的π-系统的光诱导解共轭揭示了一种反热力学多烯，它参与赫克双环化以提供[4.4.1]-螺旋桨。该级联改进了使用现有仿生策略实现的有限区域选择性，并且耐受富电子和缺电子（杂）芳基。这种方法的实用性通过紫杉二酮和鼠尾草醇的转移全合成得到了证明，这两种异构体松香二萜以前无法沿着相同的合成途径获得。
• Total Synthesis and Biological Evaluation of an Antifungal Tricyclic <i>o</i>-Hydroxy-<i>p</i>-Quinone Methide Diterpenoid
  作者：Jinhua Huang、Dylan Foyle、Xiaorong Lin、Jiong Yang

  DOI：10.1021/jo4013964

  日期：2013.9.20

  A convergent route has been developed to synthesize an antifungal tricyclic o-hydroxy-p-quinone methide diterpenoid and ana- logues. A Li/naphthalene-mediated reductive alkylation was employed for coupling beta-cyclocitral and the corresponding benzyl chloride, while a BBr3- mediated one-pot bis-demethylation and intramolecular Friedel Crafts alkylation was used to assemble the tricyclic molecular skeleton. The structure activity relationship of the diterpenoid was assessed on the basis of antiproliferation assays of the natural product and analogues against strains of pathogenic yeasts and filamentous fungi.
• Phenol Benzylic Epoxide to Quinone Methide Electron Reorganization: Synthesis of (.+-.)-Taxodone
  作者：Anthony J. Sanchez、Joseph P. Konopelski

  DOI：10.1021/jo00097a057

  日期：1994.9

  The total synthesis of(+/-)-taxodone (1) is described. The C-ring is formed by the cycloaddition of methyl acrylate with furan 8, the latter derived from isodrimenin. The C13 isopropyl group was introduced via a sulfur ylide rearrangement followed by reductive cleavage. Compound I was synthesized in 61% yield by deprotection and intramolecular oxirane opening of diacetate 31 with potassium tert-butoxide and water in THF.