(S,E)-2,6-dimethyloctyl-2,7-dien-1-ol | 177567-62-3

• 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: (S,E)-2,6-dimethyloctyl-2,7-dien-1-ol
• 英文别名: (+)-(E)-8-hydroxycitronellene；(3S)-(6E)-(+)-3,7-dimethyl-1,6-octadien-8-ol；(2E,6S)-2,6-dimethylocta-2,7-dien-1-ol
• CAS: 177567-62-3
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: ARSUYSCIFANSEF-YIXGCBLDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S,E)-2,6-dimethyloctyl-2,7-dien-1-ol 在 platinum on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 34.0h， 以85%的产率得到(2R/S,6R)-(-)-2,6-dimethyl-1-octanol
  参考文献：
  名称：

  Terpenes in organic synthesis

  摘要：

  All four stereoisomers of 2,6-dimethyloctan-1-ol, the nearest precursors of the title formates, were synthesized in five to eight stages, with configurational purity ranging from 41 to 96 %, employing a stereodivergent scheme based on the partial hydrolysis of two pseudoracemic substrates, (2RS,6R)-2,6-dimethyloct-1-yl formate and (2RS,6S)-2,6-dimethyloct-1-yl acetate, in the presence of porcine pancreatic lipase (PPL). Configurations and diastereomeric compositions of the alcohols thus obtained were determined by correlating the latter with (S,S)-4,8-dimethyldecanal, prepared on the basis of enantioselective biohydrogenation of (R)-2,6-dimethylocta-2,7-dienal with bakers' yeast, and by comparing the [alpha](D) values of the alcohols with their NMR data and/or with those of their (S)-MTPA derivatives. The attractant potency of stereoisomeric 2,6-dimethyloct-1-yl formates towards Tribolium confusum was found to vary depending on their diastereomeric composition. The configuration at C(6) exerts some influence on the stereoselectivity of the PPL-catalyzed hydrolysis of pseudoracemic 2,6-dimethyloct-1-yl formates.

  DOI：

  10.1007/bf01433762
• 作为产物：
  描述：

  (S)-8-iodo-2,6-dimethyloct-2-ene 在 叔丁基过氧化氢 、 selenium(IV) oxide 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 (S,E)-2,6-dimethyloctyl-2,7-dien-1-ol
  参考文献：
  名称：

  一种制备愈创吡啶型倍半萜类生物碱的方法

  摘要：

  本发明涉及一种制备愈创吡啶型倍半萜类生物碱的方法，该方法通过改变中间体的片段和后续官能团的改变，得到多个愈创吡啶型倍半萜类生物碱，实现了一枝蒿碱D（rupestine D）和依兰香碱（guaipydine）的不对称全合成。该方法具有灵活的发散式的合成特点，为后续筛选具有更好的生物活性的化合物提供了一种新的途径。通过该方法获得的一枝蒿碱D（rupestine D）和依兰香碱（guaipydine）与天然分离的样品进行旋光、核磁数据、高分辨质谱、单晶等对照，确定其化学结构和立体构型。

  公开号：

  CN113402461B

文献信息

• Site-Selective Functionalization of Unactivated Allylic C–H Bonds via Direct Deprotonation with KTMP: Application to the Formal Total Synthesis of (+)-Artemisinin from Amorphadiene
  作者：Nicholas A. Clanton、Nicolas A. Wilson、Eliezer Ortiz、Shawn T. Blumberg、Doug E. Frantz

  DOI：10.1021/acs.orglett.2c04145

  日期：2023.1.13

  The site-selective functionalization of unactivated allylic C–H bonds via direct deprotonation using KTMP is described. The conversion of amorphadiene to artemisinic alcohol via a simple, highly regioselective deprotonation over 4 other possible allylic sites is shown with further extrapolation to the first large-scale telescoped chemical synthesis of artemisinic acid from amorphadiene. Finally, application

  描述了通过使用 KTMP 直接去质子化未活化的烯丙基 C-H 键的位点选择性功能化。通过对 4 个其他可能的烯丙基位点的简单、高度区域选择性去质子化，将紫堇二烯转化为青蒿醇，并进一步外推到从紫杉二烯合成青蒿酸的首次大规模伸缩化学合成。最后，还强调了该方法在其他基于萜烯的天然产物中成功对未活化的烯丙基 C-H 键进行位点选择性功能化的应用。
• Regioselective Biotransformation of (+)- and (−)-Citronellene by the Larvae of Common Cutworm (Spodoptera litura)
  作者：Mitsuo Miyazawa、Shinsuke Marumoto、Atsunori Masuda、Haruki Kano、Hiromune Takechi

  DOI：10.1021/jf9009069

  日期：2009.9.9

  Terpenoids, which have many biological activities and have occurred widely in nature, can be artificially synthesized. However, regioselective oxidation of terpenoids is difficult by chemical methods. In this study, (+)- and (-)-citronellene were biotransformed with Spodoptera litura to define the mechanism of metabolism of citronellene and gain a new natural terpenoid. (+)-Citronellene was converted to (2S,3S)-3,7-dimethyl-6-octene-1,2-diol and (2R,3S)-3,7-dimethyl-6octene-1,2-diol (89.7%), (3S,6S)-(-)-3,7-dimethyl-1-octene-6,7-diol (3.8%), (3S)-(6E)-(+)-3,7-dimethyl-1,6-octadien-8-ol (4.2%), and (3S)-(6E)-(+)-3,7-dimethyl-1,6-octadien-8-oic acid (2.3%). In contrast, (-)-citronellene was converted to (2R,3R)-3,7-dimethyl-6-octene-1,2-diol and (2S,3R)-3,7dimethyl-6-octene-1,2-diol (56.3%), (+)-iridan-7,8-diol (3.5%), and (3R)-(6E)-(-)-3,7-dimethyl-1,6-octadien-8-oic acid (40.2%). The main metabolic pathway of (+)- and (-)-citronellene by larvae of S. litura was oxidized at the terminal double bond and trans-allylic methyl position. Particularly on (+)citronellene, the regioselective reaction was shown. On the oxidation of C-6, C-7, and C-8 positions, four new compounds (3S,6S)-(-)-3,7-dimethyl-1-octene-6,7-diol, (3S)-(6E)-(+)-3,7-dimethyl-1,6-octadien-8-oic acid, (+)-iridan-7,8-diol, and (3R)-(6E)-(-)-3,7-dimethyl-1,6-octadien-8-oic acid were produced in regioselective oxidation. It noted that stereoselective oxidation occurred between the enantiomers. The C-6 position was oxidized on the (+)-(3S) form, whereas cyclized and the C-7 position were oxidized on the (-)-(3R) form.
• 一种制备愈创吡啶型倍半萜类生物碱的方法
  申请人：中国科学院新疆理化技术研究所

  公开号：CN113402461B

  公开（公告）日：2023-02-03

  本发明涉及一种制备愈创吡啶型倍半萜类生物碱的方法，该方法通过改变中间体的片段和后续官能团的改变，得到多个愈创吡啶型倍半萜类生物碱，实现了一枝蒿碱D（rupestine D）和依兰香碱（guaipydine）的不对称全合成。该方法具有灵活的发散式的合成特点，为后续筛选具有更好的生物活性的化合物提供了一种新的途径。通过该方法获得的一枝蒿碱D（rupestine D）和依兰香碱（guaipydine）与天然分离的样品进行旋光、核磁数据、高分辨质谱、单晶等对照，确定其化学结构和立体构型。
• Terpenes in organic synthesis
  作者：G. D. Gamalevich、B. N. Morozov、E. P. Serebryakov

  DOI：10.1007/bf01433762

  日期：1996.1

  All four stereoisomers of 2,6-dimethyloctan-1-ol, the nearest precursors of the title formates, were synthesized in five to eight stages, with configurational purity ranging from 41 to 96 %, employing a stereodivergent scheme based on the partial hydrolysis of two pseudoracemic substrates, (2RS,6R)-2,6-dimethyloct-1-yl formate and (2RS,6S)-2,6-dimethyloct-1-yl acetate, in the presence of porcine pancreatic lipase (PPL). Configurations and diastereomeric compositions of the alcohols thus obtained were determined by correlating the latter with (S,S)-4,8-dimethyldecanal, prepared on the basis of enantioselective biohydrogenation of (R)-2,6-dimethylocta-2,7-dienal with bakers' yeast, and by comparing the [alpha](D) values of the alcohols with their NMR data and/or with those of their (S)-MTPA derivatives. The attractant potency of stereoisomeric 2,6-dimethyloct-1-yl formates towards Tribolium confusum was found to vary depending on their diastereomeric composition. The configuration at C(6) exerts some influence on the stereoselectivity of the PPL-catalyzed hydrolysis of pseudoracemic 2,6-dimethyloct-1-yl formates.