(-)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone | 252290-05-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone
• 英文别名: (4aS,5R)-4a,5-dimethyl-3,4,5,6,7,8-hexahydronaphthalen-2-one
• CAS: 252290-05-4
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: ISBAIEHOYPJLFM-SKDRFNHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone 在 对甲苯磺酸 、 原甲酸三甲酯 、 Oxone 作用下， 以51%的产率得到(4aS,5R,8S)-8-hydroxy-4a,5-dimethyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one
  参考文献：
  名称：

  环氧eujindole A的全合成

  摘要：

  首次完成了从 Eupenicillium javanicum 中分离出的结构不寻常的吲哚二萜环氧eujindole A的全合成。该合成采用后期阳离子环化策略，该策略利用了富含电子的烯烃底物。CDE 环系统通过对映选择性共轭加成/烷基化、Luche 环化和 Nozaki-Hiyama-Kishi 反应组装。重度取代的 A 环通过 Suzuki-Miyaura 偶联和阳离子环化构建，桥连的稠合 B 环通过 Prins 反应形成。

  DOI：

  10.1021/jacs.5b09198
• 作为产物：
  描述：

  2,3-dimethylcyclohexanone 在 三氟化硼乙醚 、 六甲基二硅氮烷 、 sodium iodide 作用下， 以 甲醇 、 硝基甲烷 、 乙腈 为溶剂， 反应 8.0h， 生成 (-)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone
  参考文献：
  名称：

  Total Syntheses of Anominine and Tubingensin A

  摘要：

  A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6 pi-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.

  DOI：

  10.1021/ja302765m

文献信息

• A practical and efficient preparation of (−)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone: a key intermediate in the synthesis of (−)-dehydrofukinone
  作者：Rossana A. Schenato、Éverton M. dos Santos、Beatriz S.M. Tenius、Paulo R.R. Costa、Ignez Caracelli、Julio Zukerman-Schpector

  DOI：10.1016/s0957-4166(01)00089-1

  日期：2001.3

  A novel diastereoselective route to octalone (−)-1 has been developed. The key step involves an asymmetric Michael addition of the corresponding chiral secondary enamines derived from (S)-(−)-1-phenylethylamine and (3R)-2,3-dimethylcyclohexanone to methyl vinyl ketone. This enone was successfully transformed into the eremophilane-type sesquiterpenoid (−)-dehydrofukinone.

  已经开发了一种新颖的非对映选择性途径，可以生成八-（- 1）-1。关键步骤涉及将衍生自（S）-（-）-1-苯基乙胺和（3 R）-2,3-二甲基环己酮的相应手性仲烯胺不对称迈克尔加成到甲基乙烯基酮上。该烯酮已成功转化为全草苷型倍半萜类（-）-脱氢富马酮。
• Synthesis of (−)-Nakamurol A and Assignment of Absolute Configuration of Diterpenoid (+)-Nakamurol A
  作者：Sandra Díaz、Javier Cuesta、Asensio González、Josep Bonjoch

  DOI：10.1021/jo034838r

  日期：2003.9.1

  The total synthesis of the enantiomer of the marine sponge diterpenoid nakamurol A and determination of the absolute configuration of this natural product are reported. This first synthetic entry to thelepogane-type diterpenoids involves the use of the bicyclic enone (-)-3, which after a tandem difunctionalization process and elongation of the side chain leads to the formation of the ketone (-)-13

  报道了海洋海绵二萜类纳卡莫洛尔A的对映异构体的总合成以及该天然产物的绝对构型的确定。脂环烷型二萜类化合物的第一个合成入口涉及双环烯酮（-）-3的使用，该双环烯酮在串联双官能化过程和侧链延长后导致形成酮（-）-13。从（-）-13，报道了两种对中卡那洛尔A（1）的方法：通过与乙烯基溴化镁反应的直接但非选择性的途径，以及通过伯烯丙醇20的较长但立体控制的途径，该途径被提交给进行无尖锐的环氧化反应，然后进行碲促进的还原性环氧开环级联反应。
• Overturning the Peribysin Family Natural Products Isolated from <i>Periconia byssoides</i> OUPS-N133: Synthesis and Stereochemical Revision of Peribysins A, B, C, F, and G
  作者：Paresh R. Athawale、Hanuman P. Kalmode、Zenia Motiwala、Kiran A. Kulkarni、D. Srinivasa Reddy

  DOI：10.1021/acs.orglett.0c00857

  日期：2020.4.17

  Herein we report the stereochemical revision of peribysins A, B, C, F, and G, guided by enantiospecific total synthesis starting from (+)-nootkatone. Furthermore, we reconfirmed the absolute stereochemistry of peribysin Q. The highlights of the synthesis are enone transposition and kinetic iodination resulting in separation of diastereomers. Our findings coupled with synthetic and biological data previously

  在这里，我们报告peripbysins A，B，C，F和G的立体化学修订，由（+）-Nootkatone开始的对映体特异性总合成指导。此外，我们确认了peripbysin Q的绝对立体化学。合成的亮点是烯酮转座和动力学碘化，导致非对映异构体分离。我们的发现以及Danishefsky小组先前报道的合成和生物学数据表明，peribysins A，B，C，F和G的原始立体化学分配不正确。
• Total Syntheses of Aflavazole and 14-Hydroxyaflavinine
  作者：Hailong Li、Qifeng Chen、Zhaohong Lu、Ang Li

  DOI：10.1021/jacs.6b10880

  日期：2016.12.7

  The first total syntheses of aflavazole (6) and 14-hydroxyaflavinine (8), two sterically congested indole diterpenoids, were accomplished. AlI3-promoted alkyne Prins cyclization was exploited to construct their key structural motifs. An electrocyclization-aromatization sequence assembled the pentasubstituted arene of 6, and a Stille-Migita coupling furnished the tetrasubstituted olefin of 8. The benzylic

  完成了黄酮素 (6) 和 14-羟基黄素 (8) 的首次全合成，这是两种空间拥挤的吲哚二萜。AlI3 促进的炔烃 Prins 环化被用来构建它们的关键结构基序。电环化-芳构化序列组装了 6 的五取代芳烃，Stille-Migita 偶联提供了 8 的四取代烯烃。苄基和烯丙基 CO 键分别在合成后期还原裂解。
• First stereoselective synthesis of (4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone
  作者：Xavier Cuesta、Asensio González、Josep Bonjoch

  DOI：10.1016/s0957-4166(99)00349-3

  日期：1999.8

  The synthesis of enantiomerically pure (4aS,5R)-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone (-)-1 is described for the first time. The synthesis starts from (R)-3-methylcyclohexanone and involves the preparation of piers enol lactone 6 in its enantiopure form as the key intermediate. Treatment of (+)-6 with methyl lithium followed by an intramolecular aldol reaction gives the bicyclic enone (-)-1. (C) 1999 Elsevier Science Ltd. All rights reserved.