(1S,2R,3R,6S,7S,8R)-4-methyltricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-diol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2R,3R,6S,7S,8R)-4-methyltricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-diol
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: HHZONFSXLDIGSF-OJEYFTNHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,3R,6S,7S,8R)-4-methyltricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-diol 在 咪唑 、 4-二甲氨基吡啶 、 copper(l) iodide 、 二苯醚 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.25h， 生成
  参考文献：
  名称：

  An approach toward novel bioactive natural products antroquinonols: de novo construction of the carbocyclic core

  摘要：

  A new, short, approach toward bioactive antroquinonols has been conceptualized wherein the key carbocyclic core has been readily assembled employing disposable norbornyl scaffold as the regio- and stereo-director and a Wittig olefination based strategy is projected for appending the farnesyl arm. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.09.043
• 作为产物：
  描述：

  (+/-)-6-methyl-(4arH.8acH)-1.4.4a.8a-tetrahydro-1c.4c-methano-naphthalene-quinone-(5.8) 在 甲醇 、 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 作用下， 反应 0.17h， 以81%的产率得到(1S,2R,3R,6S,7S,8R)-4-methyltricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-diol
  参考文献：
  名称：

  降冰片烯醌通过C（sp 2）-H烷基化反应的催化对映选择性脱对称

  摘要：

  与单取代对苯醌的对映选择性Diels–Alder（DA）反应是一个尚未解决的挑战。基于内消旋-DA加合物的C（sp 2）-H烷基化脱对称，提出了一种单取代的醌-DA加合物的对映选择性合成的新方法。在叔氨基-硫脲衍生物的催化下，该反应利用硝基烷烃作为烷基化剂，并产生稠密的官能化产物，该产物带有至少四个连续的立体异构中心，远离反应部位，具有出色的对映选择性。

  DOI：

  10.1021/acs.orglett.6b03168

文献信息

• Acid-Induced Rearrangement Reactions of Reduced Benzoquinone Cyclopentadiene Cycloadducts
  作者：Martin Eipert、Cäcilia Maichle-Mössmer、Martin E. Maier

  DOI：10.1021/jo026238i

  日期：2002.11.1

  Several Diels-Alder adducts between benzoquinones and cyclopentadiene were reduced to the corresponding diols 7a-c and 11. Treatment of these diols with strong acid triggered a skeletal rearrangement reaction resulting in compounds 8a-c and 12 that contain a 4,8-methanoazulene substructure. In addition, a dyotropic-like rearrangement of the tetracyclic lactone 13 to the spiro-lactone 18 was observed. Five

  苯醌和环戊二烯之间的几种Diels-Alder加合物被还原为相应的二醇7a-c和11。用强酸处理这些二醇会引发骨架重排反应，从而导致化合物8a-c和12包含4,8-甲基氮杂氮杂亚结构。另外，观察到四环内酯13向螺内酯18的类似发各向异性的重排。X射线分析支持了其中的五个结构。
• Synthesis of New Type Diacetal Trioxa-Cage Compounds via an Intramolecular Nucleophilic Addition of the Hydroxy Group to the Carbonyl Oxide Group
  作者：Hsien-Jen Wu、Ching-Shiun Chao、Chu-Chung Lin

  DOI：10.1021/jo980632s

  日期：1998.10.1

  The synthesis of diacetal trioxa-cage compounds with a new type of skeleton is reported. Ozonolysis of the diols 2a-f, 21, 24, and 33 in CH2Cl2 at -78 degrees C followed by reduction with Me2S gave the diacetal trioxa-cages 3a-f, 22, 25, and 34 in 70-80% yields, respectively. A mechanism via an intramolecular nucleophilic addition of the hydroxy group of the diols to the carbonyl oxide group is proposed for the formation of the diacetal trioxa-cages. The effect of the number of carbon atoms at the bridge of the diols on the formation of the diacetal trioxa-cage skeleton was examined. Ozonolysis of the diols 13 and 15 under the same reaction conditions gave compounds 16 and 18, respectively. No detectable amount of the trioxa-cages 17 and 19 was obtained. For the synthesis of the diacetal trioxa-cages 28a-c and 31, which possess an alkene bond intact, ozonolysis of the diols 27a-c and 30 was performed by controlling the amount of ozone.
• A New Synthesis of (-)-Aphanorphine by an Enantioconvergent Tactic
  作者：Kunio Ogasawara、Masahiro Shimizu、Takashi Kamikubo

  DOI：10.3987/com-96-s3

  日期：——
• Catalytic Enantioselective Desymmetrization of Norbornenoquinones via C(sp²)–H Alkylation
  作者：Rahul Sarkar、Santanu Mukherjee

  DOI：10.1021/acs.orglett.6b03168

  日期：2016.12.2

  The enantioselective Diels–Alder (DA) reaction with monosubstituted p-benzoquinones is an unmet challenge. A new approach for the enantioselective synthesis of monosubstituted quinone-DA adducts is presented based on C(sp2)–H alkylative desymmetrization of meso-DA adducts. Catalyzed by a tertiary amino-thiourea derivative, this reaction utilizes nitroalkanes as the alkylating agents and generates densely

  与单取代对苯醌的对映选择性Diels–Alder（DA）反应是一个尚未解决的挑战。基于内消旋-DA加合物的C（sp 2）-H烷基化脱对称，提出了一种单取代的醌-DA加合物的对映选择性合成的新方法。在叔氨基-硫脲衍生物的催化下，该反应利用硝基烷烃作为烷基化剂，并产生稠密的官能化产物，该产物带有至少四个连续的立体异构中心，远离反应部位，具有出色的对映选择性。
• An approach toward novel bioactive natural products antroquinonols: de novo construction of the carbocyclic core
  作者：Nagi Reddy Modugu、Goverdhan Mehta

  DOI：10.1016/j.tetlet.2015.09.043

  日期：2015.10

  A new, short, approach toward bioactive antroquinonols has been conceptualized wherein the key carbocyclic core has been readily assembled employing disposable norbornyl scaffold as the regio- and stereo-director and a Wittig olefination based strategy is projected for appending the farnesyl arm. (C) 2015 Elsevier Ltd. All rights reserved.