(6E,10E)-(3aS,12aR)-3-Isopropylidene-6,10,12a-trimethyl-3,3a,4,5,8,9,12,12a-octahydro-1H-cyclopentacycloundecen-2-one

• 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: (6E,10E)-(3aS,12aR)-3-Isopropylidene-6,10,12a-trimethyl-3,3a,4,5,8,9,12,12a-octahydro-1H-cyclopentacycloundecen-2-one
• 英文别名: Dolabellatrienone；(3aR,5E,9E,12aS)-3a,6,10-trimethyl-1-propan-2-ylidene-4,7,8,11,12,12a-hexahydro-3H-cyclopenta[11]annulen-2-one
• 化学式: C₂₀H₃₀O
• 分子量: 286.458
• InChiKey: YETBHHZORHIONL-SYRRJQNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  (6E,10E)-(3aS,12aR)-3-Isopropylidene-6,10,12a-trimethyl-3,3a,4,5,8,9,12,12a-octahydro-1H-cyclopentacycloundecen-2-one 在 叔丁基过氧化氢 、 selenium(IV) oxide 、 水杨酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以35%的产率得到(1R,3E,7E,11S)-13-keto-16-hydroxy-dolabella-3,7,12(18)-triene
  参考文献：
  名称：

  Semi-synthesis of oxygenated dolabellane diterpenes with highly in vitro anti-HIV-1 activity

  摘要：

  Research on dolabellane diterpenes of brown algae Dictyota spp. has shown that these diterpenoids have strong anti-HIV-1 activity, but there are not data about antiviral activity of dolabellane diterpenes isolated from octocorals, which are antipodes of those isolated from the brown algae. Dolabellanes 13-keto-1(R), 11(S)-dolabella-3(E), 7(E), 12(18)-triene (1) and beta-Araneosene (2) were isolated from the Caribbean octocoral Eunicea laciniata, and both showed low anti-HIV-1 activity and low toxicity. Since it was shown that oxygenated dolabellanes from algae have better anti-HIV-1 activity, in this work some derivatives of the main dolabellane of E. laciniata 1 were obtained by epoxidation (3), epoxide opening (4), and allylic oxidation (5). The derivatives showed significant improvement in the anti-HIV-1potency (100-fold), being compounds 3 and 5 the most active ones. Their high antiviral activities, along with their low cytotoxicity, make them promissory antiviral compounds; and it is worth noting that the absolute configuration at the ring junction in the dolabellane skeleton does not seem to be determinant in the antiviral potency of these diterpeneoids. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2014.08.019
• 作为产物：
  描述：

  反式,反式-金合欢醇 在 tris-(dibenzylideneacetone)dipalladium(0) 、 18-冠醚-6 4-二甲氨基吡啶 、 manganese(IV) oxide 、 氢氧化钾 、 sodium periodate 、 N-溴代丁二酰亚胺(NBS) 、 重铬酸吡啶 、 IBX*MPO 、 4 A molecular sieve 、 chiral oxazaborolidinium catalyst 、 2,4,6-三异丙基苯磺酰叠氮化物 、 potassium tert-butylate 、 四丁基氟化铵 、 苄基三乙基氯化铵 、 水 、 sodium hexamethyldisilazane 、 镍 、 溶剂黄146 、 过碘酸 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 正己烷 、 二氯甲烷 、 二甲基亚砜 、 1,2-二氯乙烷 、 甲苯 、 苯 为溶剂， 反应 174.88h， 生成 (6E,10E)-(3aS,12aR)-3-Isopropylidene-6,10,12a-trimethyl-3,3a,4,5,8,9,12,12a-octahydro-1H-cyclopentacycloundecen-2-one
  参考文献：
  名称：

  Palominol、Dolabellatrienone、β-Araneosene 和 Isoedunol 通过对映选择性 Diels-Alder 大环化的简明全合成

  摘要：

  报道了二萜类天然产物的多拉标烷家族的四个成员的简明全合成。所开发路线的主要特点包括首次展示了对映选择性、分子内 I 型 Diels-Alder 大环化，这是立体选择性 pi-allyl Stille 偶联反应的第一个例子，涉及法呢基衍生的中间体，这是一种用于形成二噻烷的强大新试剂具有酸敏感分子，以及基于改进的沃尔夫光化学重排的独特且高效的环收缩序列。

  DOI：

  10.1021/ja0576379

文献信息

• Semisynthesis of Dolabellane Diterpenes: Oxygenated Analogues with Increased Activity against Zika and Chikungunya Viruses
  作者：Fabián Amaya García、Claudio Cirne-Santos、Caroline de Souza Barros、Ana Maria Pinto、Maria Leonisa Sanchez Nunez、Valeria Laneuville Teixeira、Jackson A. L. C. Resende、Freddy A. Ramos、Izabel C. N. P. Paixão、Leonardo Castellanos

  DOI：10.1021/acs.jnatprod.1c00199

  日期：2021.4.23

  Brown algae and soft corals represent the main marine sources of dolabellane diterpenes. The antiviral activity of dolabellanes has been studied for those isolated from algae, whereas dolabellanes isolated from soft corals have been barely studied. In this work, a collection of dolabellane diterpenes consisting of five natural and 21 semisynthetic derivatives was constructed, and their antiviral activities

  褐藻和软珊瑚是多拉拉内二萜的主要海洋来源。已经研究了从藻类中分离出来的多拉标签内的抗病毒活性，而几乎没有研究过从软珊瑚中分离出的多拉标签。在这项工作中，构建了由 5 种天然衍生物和 21 种半合成衍生物组成的多拉拉内二萜的集合，并测试了它们对寨卡 (ZIKV) 和基孔肯雅 (CHIKV) 病毒的抗病毒活性。Dolabellatrienone ( 1 ) and (1 R ,7 R ,8 R ,11 S )-7,8-epoxy-13-keto-dolabella-3,12(18)-diene ( 2 ), 从Eunicea 中分离通过烯丙基氧化、还原、酸催化的环氧化物开环和乙酰化等反应，采用软珊瑚属获得 21 种多标签烷和多拉烷二萜。所有化合物均通过一维和二维核磁共振、质谱和 X 射线衍射实验的组合进行鉴定。测试对Vero细胞的细胞毒剂和对ZIKV和CHIKV的抗病毒活性以计算半最大有效浓度(EC
• Total synthesis of the dolabellane marine diterpenoids, claenone, palominol and dolabellatrienone
  作者：Hiroaki Miyaoka、Yutaka Isaji、Hidemichi Mitome、Yasuji Yamada

  DOI：10.1016/s0040-4020(02)01474-6

  日期：2003.1

  dolabellane diterpenoids claenone, palominol and dolabellatrienone was conducted from d-mannitol. In each case, formation of the bicyclo[2.2.1]heptane derivative by sequential Michael reaction, preparation of the tetrasubstituted cyclopentane derivative by retro-aldol reaction and cyclization of sulfone were involved as key steps.

  海洋dlabellane二萜类化合物claenone，palominol和dolabellatrienone的合成是由d-甘露糖醇进行的。在每种情况下，关键步骤包括通过顺序迈克尔反应形成双环[2.2.1]庚烷衍生物，通过逆醛醇缩合反应制备四取代的环戊烷衍生物和砜环化。
• Dolabellane-Type Diterpenoids with Antiprotozoan Activity from a Southwestern Caribbean Gorgonian Octocoral of the Genus <i>Eunicea</i>
  作者：Xiaomei Wei、Abimael D. Rodríguez、Peter Baran、Raphael G. Raptis

  DOI：10.1021/np100074r

  日期：2010.5.28

  Ten new diterpenes, 1−10, having a dolabellane skeleton were isolated from a Colombian gorgonian coral of the genus Eunicea. Their structures, as well as those of known compounds 11−18, were determined on the basis of spectroscopic analysis and, in some instances, by chemical conversion and X-ray crystallographic analysis. The absolute structure of 7 was established by chemical conversion from 11,

  从Eunicea属的哥伦比亚柳珊瑚珊瑚中分离出10 种新的二萜，1 - 10，具有多拉标烷骨架。它们的结构以及已知化合物11 - 18 的结构是在光谱分析的基础上确定的，在某些情况下，通过化学转化和 X 射线晶体学分析确定。7的绝对结构是通过化学转化从11建立的，11是已知绝对结构的共存多标签烷同源物。大多数这些二萜类化合物对原生动物寄生虫恶性疟原虫具有抗疟活性。
• First Enantioselective Total Synthesis of a Naturally Occurring Dolabellane. Revision of Absolute Configuration
  作者：E. J. Corey、Robert S. Kania

  DOI：10.1021/ja9536779

  日期：1996.1.1
• Concise total synthesis of (±)-palominol and (±)-dolabellatrienone via a dianion-accelerated oxy-cope rearrangement
  作者：E.J. Corey、Robert S. Kania

  DOI：10.1016/s0040-4039(97)10614-1

  日期：1998.2

  A short synthesis of (+/-)-palominol (1) and (+/-)-dolabellatrienone (2) starting from farnesol is reported. Noteworthy steps include an intramolecular pinacol coupling to form a 15-membered carbocyclic diol and subsequent dianion-accelerated oxy-Cope rearrangement to form the 11,5-trans-fused ring system of the dolabellanes. (C) 1998 Elsevier Science Ltd. All rights reserved.