6-oxo-6,7,8,8a,9,10-hexahydro-phenanthrene-8a-carboxylic acid methyl ester | 940004-79-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 6-oxo-6,7,8,8a,9,10-hexahydro-phenanthrene-8a-carboxylic acid methyl ester
• 英文别名: methyl 6-oxo-6,7,8,8a,9,10-hexahydrophenanthrene-8a-carboxylate；Methyl 6-oxo-7,8,9,10-tetrahydrophenanthrene-8a-carboxylate
• CAS: 940004-79-5
• 化学式: C₁₆H₁₆O₃
• 分子量: 256.301
• InChiKey: DQAAIGPSJVHUHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-oxo-6,7,8,8a,9,10-hexahydro-phenanthrene-8a-carboxylic acid methyl ester 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 10a-Hydroxymethyl-1,2,3,9,10,10a-hexahydro-phenanthren-3-ol
  参考文献：
  名称：

  γ-二甲氧基甲基环己烯-2-基的ππ* -induzierte反应：1,3-Urlagerung和Wasserstoffabstraktion durch dasα-Kohlenstoffatom †

  摘要：

  当α，β-不饱和的γ-二甲氧基甲基环己烯酮被激发到S 2（π，π*）状态时，可以观察到某些单分子反应与S 2 S 1的内部转化竞争。从S 1（n，π*）或最低的T（π，π*和n，π*）状态不会发生这些反应。它们包括formylacetal取代基的自由基清除（CF。8，9 32 + 33），γαformylacetal迁移（CF。6 27，8 30，9 34，12 37），以及涉及甲氧氢的在β位置（转移到α碳和环闭合的环化过程比照。6 28，8 31，12 38，20 40 + 41）。

  DOI：

  10.1002/hlca.19740570631
• 作为产物：
  描述：

  3,4-二氢-1(2H)-萘酮 在 sodium methylate 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 5.0h， 生成 6-oxo-6,7,8,8a,9,10-hexahydro-phenanthrene-8a-carboxylic acid methyl ester
  参考文献：
  名称：

  An approach to (±)-Lingzhiol

  摘要：

  (±)-灵芝醇已成功合成，通过七步反应从商购的5,8-二甲氧基四氢萘酮合成而成，最终产率为10.3%。该合成过程中采用了前所未有的酸催化半匹那科尔型重排反应。此外，为了构建灵芝醇的四环5/5/6/6核心结构，开发了一种新的策略，通过串联合成/重排/还原/环内酯化反应实现。

  DOI：

  10.1021/acs.orglett.6b00542

文献信息

• Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride
  作者：Valeria Justribó、Silvina C. Pellegrinet、María I. Colombo

  DOI：10.1021/jo062669f

  日期：2007.5.1

  have been conducted to investigate the reactivity of several bicyclic δ-hydroxynitriles with triflic anhydride in dichloromethane. The reactions of the analogues derived from 1-indanone and 1-tetralone lead to annulated enones. These products arise from an initial elimination reaction that generates an alkene, followed by the addition of the carbon−carbon double bond to the activated cyano group. The intramolecular

  已经进行了研究以研究几种双环δ-羟基腈与三氟甲磺酸酐在二氯甲烷中的反应性。衍生自1-茚满酮和1-四氢萘酮的类似物的反应导致环烯酮成环。这些产物产生于最初的消除反应，该反应生成烯烃，然后将碳-碳双键添加到活化的氰基上。从1-苯并亚砜获得的衍生物的分子内环化出乎意料地遵循不同的路径，从而得到环状亚氨酸酯作为主要产物。在这种情况下，活化的氰基直接被起始δ-羟基腈的羟基攻击。理论计算为观察到的反应性模式提供了理论依据。通过其质子化形式形成三氟甲磺酸盐，当环的大小由于构象效应而增加时，其随后的电离成碳正离子，以及所得的烯烃向烯酮的环化变得不那么有利。对于竞争性的对亚氨酸酯的Pinner型环化，观察到相反的趋势。还提出了在酸催化条件下由环状酰亚胺形成内酰胺的另一种机理。
• Methoxycarbonyl migration in 3-methylene-1,4-cyclohexadienes. An extension of the von Auwers rearrangement
  作者：Mehdi Boumediene、Raphaël F. Guignard、Samir Z. Zard

  DOI：10.1016/j.tet.2016.03.032

  日期：2016.6

  Upon heating, 3-methylene-1,4-cyclohexadienes possessing an alkoxycarbonyl substituent in position 6 undergo rearrangement and concomitant aromatization to give the corresponding arylacetates. This transformation represents a modification of the von Auwers rearrangement and proceeds by a radical chain mechanism. The intermediate alkoxycarbonyl radical can be intercepted allowing further useful synthetic

  加热后，在6位具有烷氧羰基取代基的3-亚甲基-1,4-环己二烯进行重排并伴随芳构化，得到相应的芳基乙酸酯。这种转变代表了冯·奥维尔（von Auwers）重排的一种变型，并通过自由基链机制进行。中间烷氧基羰基基团可以被截获，从而允许进一步有用的合成变化。
• Acetylenic cyanoenones as therapeutics for inflammation and carcinogenesis
  申请人：Honda Tadashi

  公开号：US10233146B2

  公开（公告）日：2019-03-19

  The present invention provides a compound having the structure: wherein X is C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, cyano, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenylaryl, alkenylheteroaryl, alkynylaryl, alkynylheteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, acyl, alkylhydroxy, alkylamino, alkenylamino, alkynylamino, amido, carboxyl, or carboxyl ester, or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with Y, Y is H or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with X, or forms an unsubstituted or substituted monocycle with Z; and Z is H or forms an unsubstituted or substituted monocycle with Y; wherein when X and Y are both H, then X is C2 alkenyl or C2 alkynyl, and when Y is H forms a substituted cyclohexyl, cycloheptyl with X, the cyclohexyl is other than a trisubstituted cyclohexyl bearing CH3, i-Pr and (CH2)2CO2CH3 groups or CH3, i-Pr and (CH2)3NH2, or a salt or ester thereof.

  本发明提供了一种具有以下结构的化合物： 其中 X是C1-C12烷基、C2-C12烯基、C2-C12炔基、氰基、芳基、杂芳基、烷芳基、烷基异芳基、烯芳基、烯基异芳基、炔芳基、炔基异芳基、烷氧基、烯氧基、炔氧基、芳氧基、杂芳氧基、酰基、烷基羟基、烷基氨基、烯基氨基、炔基氨基、氨基、羧基或羧基酯，或与 Y 形成未取代或取代的环丁基、环戊基、环己基、环庚基、茚或四萘、 Y 是 H，或与 X 形成未取代或取代的环丁基、环戊基、环己基、环庚基、茚满或四萘，或与 Z 形成未取代或取代的单环；和 Z 是 H，或与 Y 形成未取代或取代的单环； 其中，当 X 和 Y 均为 H 时，则 X 为 C2 烯基或 C2 炔基，而当 Y 为 H 时，则与 X 形成取代的环己基、环庚基，该环己基是三取代的环己基以外的环己基。 当 Y 为 H 与 X 形成取代的环己基、环庚基时，环己基不是含有 CH3、i-Pr 和 (CH2)2CO2 基团或 、i-Pr 和 ( )3NH2 的三取代环己基、 或其盐或酯。
• New Monocyclic, Bicyclic, and Tricyclic Ethynylcyanodienones as Activators of the Keap1/Nrf2/ARE Pathway and Inhibitors of Inducible Nitric Oxide Synthase
  作者：Wei Li、Suqing Zheng、Maureen Higgins、Rocco P. Morra、Anne T. Mendis、Chih-Wei Chien、Iwao Ojima、Dale F. Mierke、Albena T. Dinkova-Kostova、Tadashi Honda

  DOI：10.1021/acs.jmedchem.5b00393

  日期：2015.6.11

  A monocyclic compound 3 (3-ethynyl-3-methyl-6-oxocyclohexa-1,4-dienecarbonitrile) is a highly reactive Michael acceptor leading to reversible adducts with nucleophiles, which displays equal or greater potency than the pentacyclic triterpenoid CDDO in inflammation and carcinogenesis related assays. Recently, reversible covalent drugs, which bind with protein targets but not permanently, have been gaining attention because of their unique features. To explore such reversible covalent drugs, we have synthesized monocyclic, bicyclic, and tricyclic compounds containing 3 as an electrophilic fragment and evaluated them as activators of the Keap1/Nrf2/ARE pathway and inhibitors of iNOS. Notably, these compounds maintain the unique features of the chemical reactivity and biological potency of 3. Among them, a monocyclic compound 5 is the most potent in these assays while a tricyclic compound 14 displays a more robust and specific activation profile compared to 5. In conclusion, we demonstrate that 3 is a useful electrophilic fragment for exploring reversible covalent drugs.
• ACETYLENIC CYANOENONES AS THERAPEUTICS FOR INFLAMMATION AND CARCINOGENESIS
  申请人：Honda Tadashi

  公开号：US20180134654A1

  公开（公告）日：2018-05-17

  The present invention provides a compound having the structure: wherein X is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, cyano, aryl, heteroaryl, alkylaryl, alkylheteroaryl, alkenylaryl, alkenylheteroaryl, alkynylaryl, alkynylheteroaryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, heteroaryloxy, acyl, alkylhydroxy, alkylamino, alkenylamino, alkynylamino, amido, carboxyl, or carboxyl ester, or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with Y, Y is H or forms an unsubstituted or substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indane or tetralin with X, or forms an unsubstituted or substituted monocycle with Z; and Z is H or forms an unsubstituted or substituted monocycle with Y; wherein when X and Y are both H, then X is C 2 alkenyl or C 2 alkynyl, and when Y is H forms a substituted cyclohexyl, cycloheptyl with X, the cyclohexyl is other than a trisubstituted cyclohexyl bearing CH 3 , i-Pr and (CH 2 ) 2 CO 2 CH 3 groups or CH 3 , i-Pr and (CH 2 ) 3 NH 2 , or a salt or ester thereof.