(R)-2-((1R,4R,4aS,8aS)-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-1-yl)propan-1-ol

• 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: (R)-2-((1R,4R,4aS,8aS)-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-1-yl)propan-1-ol
• 英文别名: (11R)-dihydroartemisinic alcohol；(2R)-2-[(1R,4R,4aS,8aS)-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-1-yl]propan-1-ol
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: SIKURLYPEUHJFQ-QTVXIADOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  (R)-2-((1R,4R,4aS,8aS)-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-1-yl)propan-1-ol 在 氧气 、 sodium hydride 、 三氟乙酸 作用下， 以 氘代氯仿 为溶剂， 生成 (+)-10-epi-zonarene
  参考文献：
  名称：

  The role of the 12-carboxylic acid group in the spontaneous autoxidation of dihydroartemisinic acid

  摘要：

  Three of the four steps in the slow spontaneous autoxidation of dihydroartemisinic acid to artemisinin ('ene-type' reaction of molecular oxygen with the Delta(4.5) double bond, Hock cleavage of the resulting tertiary allylic hydroperoxide, oxygenation of the enol product from Hock cleavage and cyclization of the resulting vicinal hydroperoxyl-aldehyde to the 1,2,4-trioxane system of artemisinin) are shown to be assisted by the proximity of the 12-carboxylic acid functional group in dihydroartemisinic acid to the functional groups participating in these reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01192-9
• 作为产物：
  描述：

  methyl artemisinate 在 lithium aluminium tetrahydride 、 nickel dichloride 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以81%的产率得到(R)-2-((1R,4R,4aS,8aS)-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalen-1-yl)propan-1-ol
  参考文献：
  名称：

  （+）-脱氧青蒿素和（-）-脱氧脱氧青蒿素的短而立体定向合成

  摘要：

  （+）-脱氧青蒿素和（-）-脱氧脱氧青蒿素的合成是由青蒿酸或青蒿素实现的。

  DOI：

  10.1016/s0040-4039(01)93831-6

文献信息

• Selective Hydroboration–Oxidation of Terminal Alkenes under Flow Conditions
  作者：Mohamed Elsherbini、Florence Huynh、Alice Dunbabin、Rudolf K. Allemann、Thomas Wirth

  DOI：10.1002/chem.202001650

  日期：2020.9.4

  An efficient flow process for the selective hydroboration and oxidation of different alkenes using 9‐borabicyclo(3.3.1)nonane (9‐BBN) allows facile conversion in high productivity (1.4 g h−1) of amorpha‐4,11‐diene to the corresponding alcohol, which is an advanced intermediate in the synthesis of the antimalarial drug artemisinin. The in situ reaction of borane and 1,5‐cyclooctadiene using a simple

  使用9-硼环环（3.3.1）壬烷（9-BBN）进行选择性氢硼化和氧化不同烯烃的有效流程，可以轻松地以高生产率（1.4 g h -1）的无定形4,11-二烯转化为苯相应的醇，它是抗疟药青蒿素合成中的高级中间体。硼烷和1,5-环辛二烯的原位反应使用简单的流发生器证明是生成9-BBN的经济高效的解决方案。
• Photophysics of a new photosensitizer with high quantum yield of singlet oxygen generation and its application to stereo-selective synthesis of (+)-deoxoartemisinin
  作者：Kang-Kyun Wang、Kyoung-Hoon Choi、Hee-Won Shin、Bong-Jin Kim、Ji-Eun Im、Seung-Lim Oh、Nam-Soo Park、Mankil Jung、Jae-Buem Oh、Myung-Jun Lee、Hwan-Kyu Kim、Yong-Rok Kim

  DOI：10.1016/j.cplett.2009.09.081

  日期：2009.11

  n] platinum was synthesized and its photophysical study revealed that it had a high quantum yield of singlet oxygen generation. As an application study, a stereo-specific synthesis of (+)-deoxoartemisinin was performed. The induced high triplet quantum yield (0.96 ± 0.03) of [5,10,15-triphenyl-20-(4-methoxycarbonylphenyl)-porphyrin] resulted the high singlet oxygen quantum yield of 0.90 ± 0.04. The

  合成了一种新型的[5,10,15-三苯基-20-（4-甲氧基羰基苯基）-卟啉]铂光催化剂，其光物理研究表明，它具有高的单线态氧生成量子产率。作为一项应用研究，进行了（+）-脱氧青蒿素的立体特异性合成。诱导的[5,10,15-三苯基-20-（4-甲氧羰基苯基）-卟啉]的高三重态量子产率（0.96±0.03）导致了0.90±0.04的高单重态氧量子产率。将光催化作用与亚甲基蓝（MB）的光催化作用进行了比较，亚甲基蓝通常用作这些类型的有机化合物的立体特异性合成的光催化剂。合成的（+）-脱氧青蒿素的产率与单线态氧量子产率相关。
• [EN] PROCESSES FOR THE PREPARATION OF ARTEMISININ AN ITS PRECURSORS<br/>[FR] PROCÉDÉ DE PRÉPARATION D'ARTÉMISININE ET DE SES PRÉCURSEURS
  申请人：AMYRIS BIOTECHNOLOGIES INC

  公开号：WO2009088404A1

  公开（公告）日：2009-07-16

  The present invention provides processes for the preparation of artemisinin and its precursors including amorphadiene, amorphadiene epoxide, dihydroartemisinic alcohol and dihydroartemisinic acid. Specifically, artemisinin is prepared by multi-step synthetic processes from amorphadiene, amorphadiene epoxide, dihydroartemisinic alcohol or dihydroartemisinic acid. Processes for the preparation of amorphadiene, amorphadiene epoxide, dihydroartemisinic alcohol and dihydroartemisinic acid are also disclosed.

  本发明提供了制备青蒿素及其前体的方法，包括阿莫菲二烯、阿莫菲二烯环氧化物、二氢青蒿醇和二氢青蒿酸。具体来说，青蒿素通过从阿莫菲二烯、阿莫菲二烯环氧化物、二氢青蒿醇或二氢青蒿酸进行多步合成过程而制备。还公开了制备阿莫菲二烯、阿莫菲二烯环氧化物、二氢青蒿醇和二氢青蒿酸的方法。
• Chemo- and Diastereoselective Hydrosilylation of Amorphadiene toward the Synthesis of Artemisinin
  作者：Geoffrey Schwertz、Andrea Zanetti、Marllon Nascimento de Oliveira、Mario Andrés Gomez Fernandez、Zacharias Amara、Janine Cossy

  DOI：10.1021/acs.joc.0c00617

  日期：2020.8.7

  A formal synthesis of artemisinin starting from amorphadiene is described. This new route relies on the development of a catalytic chemo- and diastereoselective hydrosilylation. The practicability of this method is demonstrated by converting amorphadiene to dihydroartemisinic aldehyde using a one-pot hydrosilylation/oxidation sequence, minimizing the number of purifications and maximizing the productivity

  描述了从吗啡二烯开始的青蒿素的正式合成。这种新途径依赖于催化化学和非对映选择性氢化硅烷化的发展。该方法的实用性通过使用一锅法氢化硅烷化/氧化顺序将吗啡二烯转化为二氢青蒿醛，通过一次实际的一锅法使纯化次数最少和生产率最大化来证明。此外，该方法可以与结晶诱导的非对映选择性转化（CIDT）结合使用，以增强关键目标中间体二氢青蒿醛的光学纯度。
• Synthesis of amorpha-4,11-diene from dihydroartemisinic acid
  作者：Geoffrey Schwertz、Andrea Zanetti、Marllon Nascimento de Oliveira、Mario Andrès Gomez Fernandez、Fabienne Dioury、Janine Cossy、Zacharias Amara

  DOI：10.1016/j.tet.2018.12.050

  日期：2019.2

  Amorphadiene is a natural product involved in the biosynthesis of the antimalarial drug artemisinin. A convenient four-step synthesis of amorphadiene, starting from commercially available dihydroartemisinic acid, is reported. The targeted molecule is isolated with an overall yield of 85% on a multi-gram scale in four steps with only one chromatography.

  Amorphadiene 是一种参与抗疟药青蒿素生物合成的天然产物。报道了从市售的二氢青蒿酸开始的方便的四步合成紫穗槐二烯。目标分子以 85% 的总产率在多克规模上分四步进行分离，仅使用一次色谱法。