(4aR,8aR)-(+)-1-methylene-2-oxo-5,5,8a-trimethyldecahydronaphthalene | 108944-89-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aR,8aR)-(+)-1-methylene-2-oxo-5,5,8a-trimethyldecahydronaphthalene
• 英文别名: (4aR,8aR)-1-methylene-2-oxo-5,5,8a-trimethyl-decahydronaphthalene；(4aR,8aR)-1-methylene-2-oxo-5,5,8a-trimethyldecahydronaphthalene；(+)-12-nordrim-9-en-8-one；(4aR,8aR)-5,5,8a-trimethyl-1-methylidene-3,4,4a,6,7,8-hexahydronaphthalen-2-one
• CAS: 108944-89-4
• 化学式: C₁₄H₂₂O
• 分子量: 206.328
• InChiKey: ZZZGZBVVVQYVFZ-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 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：

  (4aR,8aR)-(+)-1-methylene-2-oxo-5,5,8a-trimethyldecahydronaphthalene 在 正丁基锂 、 氧气 、 四氯化钛 、 copper(l) chloride 、 palladium dichloride 作用下， 以 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 3.5h， 生成 13-oxo-14,15-bis-nor-ent-labd-8(17)-ene
  参考文献：
  名称：

  通过光学分辨率的Drimane倍半萜烯和Labdane二萜烯的通用合成中间体的光学拆分，可完成Copalol的两种对映异构体的全合成

  摘要：

  Copalol（6）的两个对映异构体的总合成是通过消旋二醇[（±）-4 ]的旋光拆分完成的，该消旋二醇是drimane倍半萜和拉丹烷二萜的通用合成中间体。（±）-4和Boc-1-脯氨酸之间的酯化反应得到非对映体的单酯对（5a和5b），可以通过快速柱色谱法轻松分离。拆分的5a和5b进行PDC氧化，然后进行β消除，得到旋光的烯酮（9和ent -9）。两种烯酮分别以36％的收率和（-）-转化为（+）- 6在以下五个步骤中以26％的产率获得6：（1）Sakurai反应（TiCl 4促进烯丙基硅烷的共轭加成），（2）Wittig亚甲基化，（3）Wacker氧化，（4）Horner-Emmons反应和（5）DIBAL -H减少。

  DOI：

  10.1016/s0040-4020(00)00791-2
• 作为产物：
  描述：

  香叶基丙酮 在 chromium(VI) oxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 三氯硅烷 、 水 、 四氯化锡 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙醚 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 74.17h， 生成 (4aR,8aR)-(+)-1-methylene-2-oxo-5,5,8a-trimethyldecahydronaphthalene
  参考文献：
  名称：

  Synthesis and Absolute Configuration of Zonarol. A Fungitoxic Hydroquinone from the Brown Seaweed Dictyoptfris Zonarioides(1)

  摘要：

  AbstractA total synthesis of both the enantiomers of zonarol 1 was accomplished. Measurements of the ORD‐CD spectra of two bicyclic intermediates coupled with direct comparison of the natural and synthetic zonarol 1 established the absolute configuration of the naturally occurring (+)‐zonarol 1 as 1R, 4aR, 8aR.

  DOI：

  10.1002/bscb.19860950906

文献信息

• Synthesis of decalin type chiral synthons based on enzymatic functionalisation and their application to the synthesis of (−)-ambrox and (+)-zonarol
  作者：Hiroyuki Akita、Masako Nozawa、Hiroyo Shimizu

  DOI：10.1016/s0957-4166(98)00172-4

  日期：1998.5

  Stereoselective syntheses of (−)-ambrox 2 and (+)-zonarol 3 were achieved based on the enzymatic syntheses of (8aS)- and (8aR)-decalin-type 1,3-diols 1, respectively. Non-racemic intermediates such as (8aS)-1 and (8aR)-1 were obtained based on the enantioselective hydrolyses of the phenolic acetal derivative (±)-7 by acylase I.

  （-）-ambrox 2和（+）-zonarol 3的立体选择性合成分别基于（8a S）-和（8a R）-萘烷型1,3-二醇1的酶促合成而实现。基于酚醛缩醛衍生物（±）-7被酰基转移酶I的对映选择性水解，获得了非外消旋中间体，例如（8a S）-1和（8a R）-1。
• An efficient approach to chiral nonracemic trans- and cis-decalin scaffolds for drimane and labdane synthesis
  作者：Gian Piero Pollini、Anna Bianchi、Alberto Casolari、Carmela De Risi、Vinicio Zanirato、Valerio Bertolasi

  DOI：10.1016/j.tetasy.2004.07.064

  日期：2004.10

  Optically active trans- and cis-ring junction decalinic intermediates, which represent useful precursors for the synthesis of more complex natural targets, have been conveniently prepared starting from the β-ketoester 2 obtained by standard chemistry from β-ionone and dimethyl carbonate. The chiral auxiliary (−)-menthol, easily attached to 2 through DMAP-catalyzed transesterification, allowed a clean separation

  光学活性的反式-和顺式-环结decalinic中间体，其表示用于更复杂的天然靶标合成中有用的前体，已被方便地制备从β酮酯起始2从β紫罗兰酮和碳酸二甲酯通过标准化学获得。易于通过DMAP催化的酯交换反应与2相连的手性助剂（-）-薄荷醇，可以干净地分离关键电环化步骤中获得的非对映异构体，并将其进一步精制为已经被制成十二烷基杜鹃花和拉丹烷倍半萜的手性中间体。
• Chemoenzymatic synthesis of (+)-totarol, (+)-podototarin, (+)-sempervirol, and (+)-jolkinolides E and D
  作者：Takahiro Miyake、Hideo Kigoshi、Hiroyuki Akita

  DOI：10.1016/j.tetasy.2007.11.024

  日期：2007.12

  The enzymatic resolution products [(1R,4aR,8aR)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal (8aR)-7 (98% ee) and acetate of (IS,4aS,8aS)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal} (8aS)-9 (>99% ee)] obtained by the lipase-catalyzed enantioselective acetylation of (+/-)-7 in the presence of vinyl acetate as an acyl donor were converted to the alpha,beta-unsaturated ketones (8aR)-6 and (8aS)-6, respectively. Concise syntheses of (+)-totarol 1, (+)-podototarin 2 and (+)-sempervirol 3 were achieved based on Michael reactions between (8aS)-6 and the appropriate P-keto ester followed by aldol condensation. The first chiral syntheses of (+)-jolkinolides E 4 and D 5 were achieved from (5R,10R,12R)-12-hydroxypodocarpa-8(14)-en-13-one 15 derived from (8aR)-6. (c) 2007 Elsevier Ltd. All rights reserved.
• Total synthesis of two 12-nordrimanes and the pharmacological active sesquiterpene hydroquinone yahazunol
  作者：Thorsten Laube、Winfried Beil、Karlheinz Seifert

  DOI：10.1016/j.tet.2004.11.059

  日期：2005.1

  The synthesis of two 12-nordrimanes and yahazunol was achieved via 8-oxo-12-nordrimanic acid methyl ester. The cytotoxic activity of yahazunol and seven other sesquiterpene hydroquinones and sesquiterpene quinones has been determined. (C) 2004 Elsevier Ltd. All rights reserved.
• Studies in Lipase Catalyzed Transesterifications: Synthesis of (+)-Albicanol, (+)-Albicanyl Acetate and Chiral Intermediates Useful in the Synthesis of Drimanes and Labdanes
  作者：A.T Anilkumar、Uma Sudhir、S Joly、Mangalam S Nair

  DOI：10.1016/s0040-4020(00)00096-x

  日期：2000.3

  Chiral intermediates [(-)-8, (+)-9, (-)-9, (+)-10, (-)-10, (+)-11] useful in the synthesis of drimanes and labdanes, as well as optically active albicanol 1 and albicanyl acetate 2, have been synthesized using enzymatic transesterification as the key step. (C) 2000 Elsevier Science Ltd. All rights reserved.