(8A'r)-8A'-甲基-3',4',8',8A'-四氢-2'H-螺[1,3-二氧戊环-2,1'-萘]-6'(7'H)-酮 | 117556-90-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (8A'r)-8A'-甲基-3',4',8',8A'-四氢-2'H-螺[1,3-二氧戊环-2,1'-萘]-6'(7'H)-酮
• 英文名称: (8aR)-3,4,8,8a-tetrahydro-8a-methyl-1,6(2H,7H)-naphthalenedione 1-ethylene ketal
• 英文别名: Wieland-Miescher ketone 9-ethylene ketal；(R)-Spiro[1,3-dioxolane-2,1'(2'H)-naphthalen]-6'(5'H)-one, 3',7',8',8'A-tetrahydro-8'A-methyl-；(4'aR)-4'a-methylspiro[1,3-dioxolane-2,5'-4,6,7,8-tetrahydro-3H-naphthalene]-2'-one
• CAS: 117556-90-8
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: MEFBHOLFGORPSD-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (8A'r)-8A'-甲基-3',4',8',8A'-四氢-2'H-螺[1,3-二氧戊环-2,1'-萘]-6'(7'H)-酮 在 甲基锂 、 lithium 、 L-Selectride 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 水 为溶剂， 反应 11.16h， 生成 (1S,2S,4aS,8aR)-(-)-1,2,3,4,4a,7,8,8a-octahydro-1-(hydroxymethyl)-4a-methyl-2-naphthalenol
  参考文献：
  名称：

  Total synthesis of (+)-halenaquinol and (+)-halenaquinone. Experimental proof of their absolute stereostructures theoretically determined

  摘要：

  DOI：

  10.1021/ja00233a026
• 作为产物：
  描述：

  2-methyl-2-(3-oxobutyl)cyclohexane-1,3-dione 在 三氟甲磺酸三甲基硅酯 、 pyrrolidine-2-(N-(3-(pentafluoro-λ⁶-sulfanyl)phenyl)carboxamide) 、 原甲酸三乙酯 作用下， 以 二氯甲烷 为溶剂， 反应 73.0h， 生成 (8A'r)-8A'-甲基-3',4',8',8A'-四氢-2'H-螺[1,3-二氧戊环-2,1'-萘]-6'(7'H)-酮
  参考文献：
  名称：

  恩替孕酮硫酸酯的全合成及其在NMDA受体上的生物学研究

  摘要：

  据报道，孕烯醇酮的非天然对映体的独特的不对称全合成以及对NMDA受体的生物活性的研究。不对称性是通过高度原子经济的有机催化Robinson环空法引入的。开发了一种新的环戊烷D-环的构建方法，该方法由Cu I催化的共轭物加成和氧合，然后利用持久自由基效应进行热环化。ent-孕烷醇硫酸盐是令人惊讶的仅2.6倍比天然神经类固醇活性较低。

  DOI：

  10.1021/acs.orglett.7b03838

文献信息

• Total Synthesis of (−)-Scabronine G, an Inducer of Neurotrophic Factor Production
  作者：Stephen P. Waters、Yuan Tian、Yue-Ming Li、Samuel J. Danishefsky

  DOI：10.1021/ja055220x

  日期：2005.10.1

  The total synthesis of (-)-scabronine G has been achieved in a concise manner from the (-)-Wieland-Miescher ketone. Scabronine G and its more potent methyl ester (also prepared) display activity as nonpeptidyl inducers of nerve growth factor production.

  (-)-scabronine G 的全合成已从 (-)-Wieland-Miescher 酮以简洁的方式实现。Scabronine G 及其更有效的甲酯（也已制备）显示出作为神经生长因子产生的非肽基诱导剂的活性。
• Synthesis of Scabronines and Analogues Thereof
  申请人：Danishefsky Samuel J.

  公开号：US20090186940A1

  公开（公告）日：2009-07-23

  A novel synthesis of scabronines, which are related to a broader class of angularly fused tricyclic diterpenoids known as cyathanes, is provided. Scabronine G, its methyl ester derivative, and other analogs have been shown to have neurotrophic activity. Therefore, these compounds are particularly useful in treating neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, Huntington's diseases, etc. The invention provides for the synthesis of scabronines as well as analogs thereof. Pharmaceutical compositions and method of using the inventive compounds are also provided.

  提供了一种新型的斯卡布罗宁合成方法，斯卡布罗宁与一类更广泛的角融合的三环二萜类化合物——赛萨烷相关。斯卡布罗宁G、其甲酯衍生物以及其他类似物已被证明具有神经营养活性。因此，这些化合物在治疗神经退行性疾病，如阿尔茨海默病、帕金森病、亨廷顿病等疾病中特别有用。本发明提供了斯卡布罗宁及其类似物的合成方法。还提供了含有本发明的化合物的药物组合物和使用方法。
• Enantioselective Synthesis of the Antiinflammatory Agent (−)-Acanthoic Acid
  作者：Taotao Ling、Chinmay Chowdhury、Bryan A. Kramer、Binh G. Vong、Michael A. Palladino、Emmanuel A. Theodorakis

  DOI：10.1021/jo0159035

  日期：2001.12.1

  An enantioselective synthesis of the potent antiinflammatory agent (-)-acanthoic acid (1) is described. The successful strategy departs from (-)-Wieland-Miescher ketone (10), which is readily available in both enantiomeric forms and constitutes the starting point toward a fully functionalized AB ring system of 1. Conditions were developed for a regioselective double alkylation at the C4 center of the

  描述了有效的抗炎药（-）-棘酸（1）的对映选择性合成。成功的策略与（-）-Wieland-Miescher酮（10）背离，后者易于以两种对映体形式使用，构成了向完全功能化的AB环系统1的起点。 A环的C4中心，生成化合物32为单个立体异构体。C环1的构建是通过含硫二烯43与甲基丙烯醛（36）之间的Diels-Alder反应完成的，脱硫和进一步官能化后生成合成的棘酸。
• Interleukin-1 and tumor necrosis factors-&agr; modulators, syntheses of said modulators and methods of using modulators
  申请人：Nereus Pharmaceuticals, Inc.

  公开号：US06365768B1

  公开（公告）日：2002-04-02

  Novel compounds are disclosed that have the chemical structure of Formula (IIB), and its prodrug esters and acid-addition salts, and that are useful as Interleukin-1 and Tumor Necrosis Factor-&agr; modulators, and thus are useful in the treatment of various diseases. wherein the R groups include the following: R1 is selected from the group consisting of hydrogen, a halogen, COOH, C1-C12 carboxylic acids, C1-C12 acyl halides, C1-C12 acyl residues, C1-C12 esters, C1-C12 secondary amides, (C1-C12)(C1-C12) tertiary amides, C1-C12 alcohols, (C1-C12)( C1-C12) ethers, C1-C12 alkyls, C1-C12 substituted alkyls, C2-C12 alkenyls, C2-C12 substituted alkenyls; R2 is selected from hydrogen, a halogen, C1-C12 alkyl, C1-C12 substituted alkyls, C2-C12 alkenyl, C2-C12 substituted alkenyl, C2-C12 alkynyl, and C1-C12 acyl, and C5-C12 aryl. R3, R4, R5, R7, R8, and R11-R13 are each separately selected from hydrogen, a halogen, C1-C12 alkyl, C1-C12 substituted alkyls, C2-C12 alkenyl, C2-C12 substituted alkenyl, C2-C12 alkynyl, and C5-C12 aryl. R6 is selected from hydrogen, a halogen, C1-C12 alkyls, C1-C12 substituted alkyls, C2-C12 alkenyls, C2-C12 substituted alkenyl and C2-C12 alkynyl. R10 is selected from hydrogen, a halogen, CH2, C1-C6 alkyl, C1-C6 substituted alkyl, C2-C6 alkenyl, C2-C6 substituted alkenyl, C1-C12 alcohol, and C5-C12 aryl.

  揭示了具有化学结构为Formula (IIB)的新化合物，以及其前药酯和酸加成盐，这些化合物可用作白细胞介素-1和肿瘤坏死因子-α调节剂，因此在治疗各种疾病中很有用。 其中R基团包括以下内容：R1选自氢、卤素、COOH、C1-C12羧酸、C1-C12酰卤、C1-C12酰基、C1-C12酯、C1-C12次酰胺、(C1-C12)(C1-C12)三级酰胺、C1-C12醇、(C1-C12)(C1-C12)醚、C1-C12烷基、C1-C12取代烷基、C2-C12烯基、C2-C12取代烯基；R2选自氢、卤素、C1-C12烷基、C1-C12取代烷基、C2-C12烯基、C2-C12取代烯基、C2-C12炔基和C1-C12酰基、以及C5-C12芳基。R3、R4、R5、R7、R8和R11-R13分别选自氢、卤素、C1-C12烷基、C1-C12取代烷基、C2-C12烯基、C2-C12取代烯基、C2-C12炔基和C5-C12芳基。R6选自氢、卤素、C1-C12烷基、C1-C12取代烷基、C2-C12烯基、C2-C12取代烯基和C2-C12炔基。R10选自氢、卤素、CH2、C1-C6烷基、C1-C6取代烷基、C2-C6烯基、C2-C6取代烯基、C1-C12醇和C5-C12芳基。
• A Chiral-Pool-Based Approach to the Core Structure of (+)-Hyperforin
  作者：Jean-Alexandre Richard、David Y.-K. Chen

  DOI：10.1002/ejoc.201101629

  日期：2012.1

  Asymmetric entry to the bicyclic core structure of (+)-hyperforin is presented. The developed synthetic strategy features a carefully orchestrated stereochemical relay from the single chiral center residing within (–)-Wieland–Miescher ketone and an intramolecular aldol reaction to cast the [3.3.1] bicyclic scaffold found in a diverse array of polycyclic polyprenylated acylphloroglucinols.

  不对称进入 (+)-hyperforin 的双环核心结构。所开发的合成策略具有精心编排的立体化学中继，来自驻留在 (-)-Wieland-Miescher 酮内的单个手性中心和分子内醛醇反应，以铸造在各种多环聚异戊二烯化酰基间苯三酚中发现的 [3.3.1] 双环支架。