(S)-1,3-dihydroxy-3,7-dimethyl-6-octen-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: (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one
• 英文别名: (s)-3,7-Dimethyl-2-oxo-6-octene-1,3-diol；(3S)-1,3-dihydroxy-3,7-dimethyloct-6-en-2-one
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: FOMPNSJZRJXFMV-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-溴苯甲酰氯 、 (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到(S)-3-hydroxy-3,7-dimethyl-2-oxo-6-octenyl 4-bromobenzoate
  参考文献：
  名称：

  Catalytic asymmetric synthesis of the Colorado potato beetle pheromone and its enantiomer

  摘要：

  An efficient catalytic asymmetric synthesis of the CPB pheromone [(S)-1,3-dihydroxy-3,7-dimethy1-6-octen-2-one] and its enantiomer was accomplished with 99% ee and in gram quantities from geraniol. The key steps in this procedure involve Sharpless asymmetric epoxidation and recrystallization of the 4-bromobenzoate from the CPB pheromone to improve its enantiomeric purity. Furthermore, the absolute configuration of the CPB pheromone enantiomer was confirmed as (R) for the first time by the X-ray crystallographic structure of its benzoate. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.12.018
• 作为产物：
  描述：

  6-甲基-5-庚烯-2-酮 在 (R,R)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminoaluminum(III) chloride 、 碳酸氢钠 、 对甲苯磺酸 、 乙氧甲酰基亚甲基三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 33.0h， 生成 (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one
  参考文献：
  名称：

  Me2(CH2Cl)SiCN：双功能氰化试剂，用于通过酮氰基硅烷化合成带有氯甲基酮部分的叔醇

  摘要：

  我们报告了一种新型双功能氰化试剂 Me2(CH2Cl)SiCN，它为通过对映选择性酮氰硅烷化合成具有氯甲基酮部分的叔醇的一锅法顺序合成铺平了道路。该方法有助于科罗拉多马铃薯甲虫 (S)-CPB 聚集信息素的克级对映选择性全合成。

  DOI：

  10.1021/jacs.6b05601

文献信息

• Organic Synthesis in Pheromone Science
  作者：Kenji Mori

  DOI：10.3390/10091023

  日期：——

  Examples are given to illustrate the use of chemical and/or enzymatic asymmetric reactions in the synthesis of the new pheromones of the broad-horned flour beetle, flea beetle, currant stem girdler and Colorado potato beetle. The relationships between stereochemistry and bioactivity among pheromones are summarized to emphasize biodiversity as revealed in pheromone perception.

  给出了例子来说明化学和/或酶促不对称反应在合成宽角面粉甲虫、跳虫、黑加仑茎切割虫和科罗拉多土豆甲虫的新信息素中的应用。总结了信息素中立体化学与生物活性之间的关系，以强调在信息素感知中揭示的生物多样性。
• Synthesis of the aggregation pheromone of the Colorado potato beetle from its degradation product
  作者：Weronika Wacławczyk-Biedroń、Bożena Frąckowiak-Wojtasek、Daniel Strub、Magdalena Rzechak、Hubert Wojtasek

  DOI：10.1016/j.bmcl.2015.06.083

  日期：2015.9

  Incubation of the Colorado potato beetle aggregation pheromone, (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one, with antennal or leg extracts from this beetle gave 6-methyl-5-hepten-2-one as the major product. This ketone was used as a substrate in a stereoselective synthesis of the pheromone. It was attached to the butanediacetal of glycolic acid with good stereoselectivity and the desired isomer was

  将科罗拉多马铃薯甲虫聚集信息素（S）-1,3-二羟基-3,7-二甲基-6-辛烯-2-酮与该甲虫的触角或腿部提取物一起孵育，得到6-甲基-5-庚烯-二合一为主要产品。该酮用作信息素的立体选择性合成中的底物。将其以良好的立体选择性连接到乙醇酸的丁二缩醛上，并通过在硅胶上纯化该反应的产物来进一步富集所需的异构体。
• Alternative Synthesis of the Colorado Potato Beetle Pheromone
  作者：Juan A. Faraldos、Robert M. Coates、José-Luis Giner

  DOI：10.1021/jo4017056

  日期：2013.10.18

  involves a 6-endo epoxide ring-opening with ester participation that simultaneously inverts the 3R-configuration of the (3R)-2,3-epoxy-2-fluoroprenyl acetate intermediate and installs the ketone functionality of the semiochemical. Extensive NMR studies validate the proposed 6-endo mechanism of the featured rearrangement, which under anhydrous conditions resulted in the formation of two bicyclic 1,3-dioxan-5-ones

  雄性科罗拉多马铃薯甲虫分泌的信息素的简明制剂[即。(3 S )-1,3-二羟基-3,7-二甲基-6-辛烯-2-one]从2-氟橙花醇或2-氟香叶醇开始，分四步完成。合成中的关键步骤涉及酯参与的 6-内环氧化物开环，同时反转(3 R )-2,3-环氧-2-氟异戊二烯乙酸酯中间体的 3 R-构型并安装符号化学。广泛的 NMR 研究验证了所提出的特征重排的 6-endo 机制，该机制在无水条件下通过前所未有的分子内 Prins 环化形成两个双环 1,3-二恶烷-5-酮。
• A protecting group-free synthesis of the Colorado potato beetle pheromone
  作者：Zhongtao Wu、Manuel Jäger、Jeffrey Buter、Adriaan J Minnaard

  DOI：10.3762/bjoc.9.273

  日期：——

  A novel synthesis of the aggregation pheromone of the Colorado potato beetle, Leptinotarsa decemlineata, has been developed based on a Sharpless asymmetric epoxidation in combination with a chemoselective alcohol oxidation using catalytic [(neocuproine)PdOAc]₂OTf₂. Employing this approach, the pheromone was synthesized in 3 steps, 80% yield and 86% ee from geraniol.

  基于Sharpless不对称环氧化和化学选择性醇氧化的组合，利用催化[(neocuproine)PdOAc]₂OTf₂，开发了一种新的合成科罗拉多马铃薯甲虫聚集信息素的方法。采用这种方法，从香叶醇出发，经过3个步骤，得到甲虫聚集信息素，产率为80%，ee为86%。
• Versatile Amine-Promoted Mild Methanolysis of 3,5-Dinitrobenzoates and Its Application to the Synthesis of Colorado Potato Beetle Pheromone
  作者：Yumiko Yamano、Haruna Sasaki、Akimori Wada

  DOI：10.1248/cpb.c17-00462

  日期：——

  A mild deacylation method for 3,5-dinitrobenzoates using methanolic solutions of amines, such as dialkylamines, was developed. The method's versatility was confirmed by applying it to synthesizing a key intermediate for Colorado potato beetle pheromone.

  开发了使用胺（例如二烷基胺）的甲醇溶液温和的3,5-二硝基苯甲酸酯脱酰方法。通过将该方法应用于科罗拉多马铃薯甲虫信息素的关键中间体的合成，证实了该方法的多功能性。