(1S,4R,5S,8R,9R,11S,12S)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.0.^4,120^8,12]pentadecane-2-carbaldehyde | 339530-87-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1S,4R,5S,8R,9R,11S,12S)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.0.^4,120^8,12]pentadecane-2-carbaldehyde
• 英文别名: (1R,4S,5R,8S,9R,11R,12R)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.04,12.08,12]pentadecane-9-carbaldehyde
• CAS: 339530-87-9
• 化学式: C₁₅H₂₂O₅
• 分子量: 282.337
• InChiKey: AQBOGOMTXRZDEI-CAJFQKGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S,4R,5S,8R,9R,11S,12S)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.0.^4,120^8,12]pentadecane-2-carbaldehyde 在 二氯乙酸 、 四丁基氟化铵 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 二甲基亚砜 、 甲苯 为溶剂， 反应 24.0h， 生成 2,2,2-trifluoro-1-[(1S,4R,5S,8R,9R,11R,12S)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.0.^4,120^8,12]pentadec-9-yl]-1-ethanone
  参考文献：
  名称：

  Anhydrodihydroartemisinin and Its 10-Trifluoromethyl Analogue:  Access to Novel D-Ring-Contracted Artemisinin Trifluoromethyl Ketones

  摘要：

  The preparation of the 10-trifluoromethyl hydroartemisinin, followed by dehydration, afforded the trifluoromethyl analogue 2 of anhydrodihydroartemisinin 1. The reactivity of these two glycals of artemisinin were compared in epoxidation and halogenation reactions. Iodination of glycal 1 in water and the further rearrangement of the produced iodo hemiacetal provided the new D-ring-contracted aldehyde 8alpha, where the methyl at C-9 is beta. Epoxidation of 10-trifluoromethyl anhydrodihydroartemisinin 2 stereoselectively provided the beta-epoxy ether 11 in high yield. When treated with hexafluoro-2-propanol or trifluoroethanol, 11 readily underwent a rearrangement yielding to the D-ring-contracted trifluoromethyl ketone 9alpha with retention of configuration at C-9.

  DOI：

  10.1021/jo016091f
• 作为产物：
  描述：

  脱水二氢青蒿素 在 phosphate buffer 、 碘 作用下， 以 水 、 叔丁醇 为溶剂， 反应 24.0h， 以57%的产率得到(1S,4R,5S,8R,9R,11S,12S)-1,5,9-trimethyl-10,13,14,15-tetraoxatetracyclo[9.3.1.0.^4,120^8,12]pentadecane-2-carbaldehyde
  参考文献：
  名称：

  Anhydrodihydroartemisinin and Its 10-Trifluoromethyl Analogue:  Access to Novel D-Ring-Contracted Artemisinin Trifluoromethyl Ketones

  摘要：

  The preparation of the 10-trifluoromethyl hydroartemisinin, followed by dehydration, afforded the trifluoromethyl analogue 2 of anhydrodihydroartemisinin 1. The reactivity of these two glycals of artemisinin were compared in epoxidation and halogenation reactions. Iodination of glycal 1 in water and the further rearrangement of the produced iodo hemiacetal provided the new D-ring-contracted aldehyde 8alpha, where the methyl at C-9 is beta. Epoxidation of 10-trifluoromethyl anhydrodihydroartemisinin 2 stereoselectively provided the beta-epoxy ether 11 in high yield. When treated with hexafluoro-2-propanol or trifluoroethanol, 11 readily underwent a rearrangement yielding to the D-ring-contracted trifluoromethyl ketone 9alpha with retention of configuration at C-9.

  DOI：

  10.1021/jo016091f

文献信息

• Synthesis and biological evaluation of a series of non-hemiacetal ester derivatives of artemisinin
  作者：Nonkululeko H. Zuma、Frans J. Smit、Carmen de Kock、Jill Combrinck、Peter J. Smith、David D. N'Da

  DOI：10.1016/j.ejmech.2016.07.027

  日期：2016.10

  ester derivatives of artemisinin were synthesized and evaluated for their in vitro antiplasmodial and anticancer activities as well as cytotoxicities. These esters were synthesized through the reaction of acid anhydrides, or acid chlorides with artemisinin derived alcohol. In vitro antiplasmodial activity assessments were conducted against intraerythrocytic NF54 and Dd2 Plasmodium falciparum strains. Cytotoxicities

  为了提高目前临床使用的青蒿素的功效和稳定性，合成了一系列青蒿素的非半缩醛酯衍生物，并评估了它们的体外抗疟原虫和抗癌活性以及细胞毒性。这些酯是通过酸酐或酰氯与青蒿素衍生的醇反应合成的。针对红细胞内 NF54 和 Dd2恶性疟原虫进行了体外抗疟原虫活性评估菌株。使用正常人胎肺成纤维细胞 (WI-38) 和中国仓鼠卵巢 (CHO) 哺乳动物细胞系评估细胞毒性，同时使用由肾 (TK10)、黑色素瘤 (UACC62) 组成的三种细胞系的面板测试抗癌活性和乳腺癌（MCF7）癌细胞。大多数化合物被发现对乳腺癌细胞系有活性。由于发现大多数化合物的抗疟原虫活性仅与青蒿琥酯相当，因此该研究没有产生任何具有显着改善抗疟功效的酯，也没有提供任何有希望的抗肿瘤命中。然而，根据这项研究的结果，确定了与临床使用的青蒿素相比具有良好安全性和更高热稳定性的化合物。苯甲酸酯衍生物11 被发现具有与双氢青蒿素相当的抗疟活性，随
• Fluoro Artemisinins: Difluoromethylene Ketones
  作者：Fatima Chorki、Fabienne Grellepois、Benoit Crousse、Michèle Ourévitch、Danièle Bonnet-Delpon、Jean-Pierre Bégué

  DOI：10.1021/jo0158579

  日期：2001.11.1

  corresponding difluoromethylene ketol adducts in good yields. Similar Lewis acid catalyzed reactions of dihydroartemisinin acetate with the difluoroenoxysilanes provided the 10-substituted difluoromethylene ketones in good to moderate yields. Interestingly enough, the course and the stereochemistry of these reactions are highly dependent on the nature of the Lewis acids used; the addition reaction was accompanied

  在 BF(3).Et(2)O 存在下，衍生自脱水二氢青蒿素的环缩醛与 gem-二氟烯氧基硅烷的反应以良好的产率提供了相应的二氟亚甲基酮醇加合物。类似的路易斯酸催化二氢青蒿素乙酸酯与二氟烯氧基硅烷的反应以良好至中等的产率提供了 10-取代的二氟亚甲基酮。有趣的是，这些反应的过程和立体化学高度依赖于所用路易斯酸的性质。加成反应伴随着 C-9 处的差向异构化，C-10 处的立体化学取决于所用的二氟烯氧基硅烷。最好的结果是使用 SnCl(4) 获得高立体选择性的 9alpha,10beta 立体异构体。当 0。
• Ring-contracted artemisinin derivatives: stereoselective reaction of anhydrodihydroartemisinin towards halogenating reagents
  作者：Fabienne Grellepois、Danièle Bonnet-Delpon、Jean-Pierre Bégué

  DOI：10.1016/s0040-4039(01)00140-x

  日期：2001.3

  Reaction of anhydrodihydroartemisinin 1 with halogenating reagents and further rearrangement of adducts into ring-contracted aldehydes has been revisited. The stereochemistry of reactions with iodine is opposite to that with bromine, and allowed the preparation of the new aldehyde 4 with conservation of the configuration of starting artemisinin at C-9. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Anhydrodihydroartemisinin and Its 10-Trifluoromethyl Analogue:  Access to Novel D-Ring-Contracted Artemisinin Trifluoromethyl Ketones
  作者：Fabienne Grellepois、Fatima Chorki、Benoit Crousse、Michèle Ourévitch、Danièle Bonnet-Delpon、Jean-Pierre Bégué

  DOI：10.1021/jo016091f

  日期：2002.2.1

  The preparation of the 10-trifluoromethyl hydroartemisinin, followed by dehydration, afforded the trifluoromethyl analogue 2 of anhydrodihydroartemisinin 1. The reactivity of these two glycals of artemisinin were compared in epoxidation and halogenation reactions. Iodination of glycal 1 in water and the further rearrangement of the produced iodo hemiacetal provided the new D-ring-contracted aldehyde 8alpha, where the methyl at C-9 is beta. Epoxidation of 10-trifluoromethyl anhydrodihydroartemisinin 2 stereoselectively provided the beta-epoxy ether 11 in high yield. When treated with hexafluoro-2-propanol or trifluoroethanol, 11 readily underwent a rearrangement yielding to the D-ring-contracted trifluoromethyl ketone 9alpha with retention of configuration at C-9.