3,10-dihydroxy-6,12-di-iso-propyl-3,10-dimethyltricyclo[6.2.2.0^2,7]dodeca-5,11-diene-4,9-dione

• 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: 3,10-dihydroxy-6,12-di-iso-propyl-3,10-dimethyltricyclo[6.2.2.0^2,7]dodeca-5,11-diene-4,9-dione
• 英文别名: 3,10-Dihydroxy-5,11-dielmenthadiene-4,9-dione；(1S,2S,3R,7R,8S,10R)-3,10-dihydroxy-3,10-dimethyl-6,12-di(propan-2-yl)tricyclo[6.2.2.02,7]dodeca-5,11-diene-4,9-dione
• 化学式: C₂₀H₂₈O₄
• 分子量: 332.44
• InChiKey: YNYHPBIGKWCFOA-GNNUITGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,10-dihydroxy-6,12-di-iso-propyl-3,10-dimethyltricyclo[6.2.2.0^2,7]dodeca-5,11-diene-4,9-dione 以 甲醇 为溶剂， 反应 24.0h， 以81%的产率得到4,11-dihydroxy-7,8-di-iso-propyl-4,11-dimethylpentacyclo[6.4.0.0^2,7.0^3,10.0^6,9]dodecane-5,12-dione
  参考文献：
  名称：

  Regio- and stereoselectivities in Diels–Alder cyclodimerizations of orthoquinonoid cyclohexa-2,4-dienones

  摘要：

  The [4+2] cyclodimerization of cyclohexa-2,4-dienone derivatives of the orthoquinone monoketal and orthoquinol types has been the topic of numerous investigations over the last 50 years in the aim of rationalizing the extraordinary level of regio-, site-, and stereoselectivities observed in these processes. In particular, the double diastereo-pi-facial differentiation expressed in cyclodimerizations of chiral orthoquinols (i.e., 6-alkyl-6-hydroxycyclohexa-2,4-dienones) is an important aspect of these transformations, for they relate to the construction of several natural products. The experimental and theoretical results that are described in this article offer a comprehensive understanding of the factors controlling these site- specific regio- and diastereoselectivities. Our interpretation of these results relies on a combination of Wood-ward-Hoffmann and Salem-Houk secondary orbital interactions and Cieplak-type hyperconjugative effects in bispericyclic C-2-symmetric transition states. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.035
• 作为产物：
  描述：

  香芹酚 在 双氧水 、 sodium carbonate 、 9-propyl-9-azatricyclo[9.4.0.0^2,7]pentadeca-1⁽¹¹⁾,2,4,6,8,12,14-heptaen-9-ium bromide 作用下， 以 水 、 乙腈 为溶剂， 反应 18.0h， 以59%的产率得到3,10-dihydroxy-6,12-di-iso-propyl-3,10-dimethyltricyclo[6.2.2.0^2,7]dodeca-5,11-diene-4,9-dione
  参考文献：
  名称：

  氧氮丙啶催化邻羟基苯酚脱芳构化有机催化对映选择性合成双环[2.2.2]辛烯酮**

  摘要：

  描述了苯酚的对映选择性、oxaziridinium 催化的邻羟基脱芳构化-[4+2] 二聚反应。这种具有经典挑战性的转化成功地用于合成具有高对映选择性的双（单萜）（+）-双香芹酚和细菌代谢物（-）-双（2,6-二甲苯酚）。我们简单的有机催化系统可耐受多种苯酚取代模式和邻位取代基。

  DOI：

  10.1002/anie.202205278

文献信息

• Asymmetric Hydroxylative Phenol Dearomatization through In Situ Generation of Iodanes from Chiral Iodoarenes and<i>m</i>-CPBA
  作者：Stéphane Quideau、Gildas Lyvinec、Mélanie Marguerit、Katell Bathany、Aurélie Ozanne-Beaudenon、Thierry Buffeteau、Dominique Cavagnat、Alain Chénedé

  DOI：10.1002/anie.200901039

  日期：2009.6.8

  ′I′ is all the hype: A twofold excess of iodoarene in the title reaction leads to ortho‐quinols in good yields, whereas organocatalytic versions of this reaction enable subsequent epoxidation in a regio‐ and diastereoselective fashion. Chiral iodobiarenes led to enantioselectivities up to 50 % ee. m‐CPBA=meta‐chloroperoxybenzoic acid.

  “ I”全是炒作：标题反应中碘芳烃的两倍过量导致邻喹啉收率高，而该反应的有机催化形式使得随后的环氧化反应可以进行区域选择性和非对映选择性。手性碘伏二烯导致对映体选择性高达ee的50％  。m -CPBA =间-氯过氧苯甲酸。
• Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes
  作者：Cyril Bosset、Romain Coffinier、Philippe A. Peixoto、Mourad El Assal、Karinne Miqueu、Jean-Marc Sotiropoulos、Laurent Pouységu、Stéphane Quideau

  DOI：10.1002/anie.201403571

  日期：2014.9.8

  The long‐standing quest for chiral hypervalent organoiodine compounds (i.e., iodanes) as metal‐free reagents for asymmetric synthesis continues. Although remarkable progress has recently been made in organoiodine‐catalyzed reactions using a terminal oxidant in stoichiometric amounts, there is still a significant need for “flaskable” chiral iodane reagents. Herein, we describe the synthesis of new iodobinaphthyls

  长期以来，对手性高价有机碘化合物（即碘）作为不对称合成的无金属试剂的追求仍在继续。尽管最近使用化学计量的末端氧化剂在有机碘催化的反应中取得了显着进展，但是仍然非常需要“易燃”的手性碘试剂。在本文中，我们描述的新iodobinaphthyls和iodobiphenyls，他们成功的和有选择性的DMDO介导的氧化的合成成任一λ 3 -或λ 5个-iodanes，和它们的能力的评估，以促进非对称hydroxylative苯酚脱芳构化（HPD）的反应。最值得注意的是，一个C 2 -symmetrical biphenylicλ 5碘烷促进了HPD诱导的单萜百里酚转化为相应的基于邻喹啉的[4 + 2]环二聚体（即bis（thymol）），对映体过量高达94％。
• Efficient Access to Orthoquinols and Their [4 + 2] Cyclodimers via SIBX-Mediated Hydroxylative Phenol Dearomatization
  作者：Nathalie Lebrasseur、Julien Gagnepain、Aurélie Ozanne-Beaudenon、Jean-Michel Léger、Stéphane Quideau

  DOI：10.1021/jo0708893

  日期：2007.8.1

  efficiently mediates the hydroxylative dearomatization of various 2-alkylphenols and napthols into orthoquinols or their [4 + 2] cyclodimers. Reactions are typically run at room temperature using SIBX as a suspension in THF. Using these conditions, natural products such as the cyclodimer of the terpene carvacrol and, for the first time, the shikimate-derived (±)-grandifloracin were prepared in one step from

  SIBX，λ的非爆炸性制剂5 -iodane 2- iodoxybenzioc苯甲酸（IBX），安全和有效地介导各种2-烷基酚和napthols的脱芳构化hydroxylative成orthoquinols或它们的[4 + 2] cyclodimers。反应通常在室温下使用SIBX作为THF的悬浮液进行。在这些条件下，一步一步地从其各自的酚类前体中制备了天然产物，例如萜烯香芹酚的环二聚体，以及首次从sh草酸酯衍生的（±）-大花青素。
• 4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols
  作者：Muhammet Uyanik、Tatsuya Mutsuga、Kazuaki Ishihara

  DOI：10.1002/anie.201612463

  日期：2017.3.27

  dearomatization of 2‐substituted phenols to either 1,2‐benzoquinols or their cyclodimers, catalyzed by 4,5‐dimethyl‐2‐iodoxybenzenesulfonic acid with Oxone, has been developed. Natural products such as biscarvacrol and lacinilene C methyl ether could be synthesized efficiently under mild reaction conditions. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of

  已开发了由4,5-二甲基-2-碘氧基苯磺酸与Oxone催化的2-取代酚选择性地羟基化脱芳香化为1,2-苯并喹啉或其环二聚体。在温和的反应条件下，可以有效地合成天然产物，例如联萘香酚和乳香油基C甲醚。此外，通过在苯酚的2位引入三烷基甲硅烷基甲基取代基，可以进一步提高反应速度和位点选择性。通过[4 + 2]环加成级联反应可以将相应的1,2-喹诺酚转化为各种有用的结构基序。
• Facile synthesis of amino acid-derived novel chiral hypervalent iodine(V) reagents and their applications
  作者：Yasushi Yoshida、Akina Magara、Takashi Mino、Masami Sakamoto

  DOI：10.1016/j.tetlet.2016.10.016

  日期：2016.11

  Amino acid-derived novel chiral hypervalent iodine(V) reagents were synthesized from the corresponding chiral iodoarenes through DMDO oxidations. Their oxidation states were determined by the 13C NMR chemical shifts of the ipso-carbon of the iodine atom, HRMS analysis, and elemental analyses. They were applied to the enantioselective hydroxylative dearomatization/[4+2]-dimerization cascade reactions

  从相应的手性碘芳烃通过DMDO氧化合成了氨基酸衍生的新型手性高价碘试剂。它们的氧化态由碘原子的ipso-碳的13 C NMR化学位移，HRMS分析和元素分析确定。将它们用于苯酚衍生物的对映选择性羟基化脱芳香化/ [4 + 2]-二聚级联反应，得到所需产物，其ee最高为58％。