cis-theaspirane | 43126-22-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: cis-theaspirane
• 英文别名: theaspirane A；theaspirane；1-Oxaspiro(4.5)dec-6-ene, 2,6,10,10-tetramethyl-, (2R,5R)-rel-；(2R,5R)-2,6,6,10-tetramethyl-1-oxaspiro[4.5]dec-9-ene
• CAS: 43126-22-3
• 化学式: C₁₃H₂₂O
• 分子量: 194.317
• InChiKey: GYUZHTWCNKINPY-YPMHNXCESA-N

物化性质

• 沸点：
  254.1±19.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)
• LogP：
  4.139 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-theaspirane 在 氧气 、 tetraphenylporphyrin 作用下， 以 氘代氯仿 为溶剂， 以95%的产率得到(2R*,5R*)-7-hydroperoxy-2,10,10-trimethyl-6-methylene-1-oxaspiro[4.5]decane
  参考文献：
  名称：

  Studies towards the synthetic applicability of biocatalytic allylic oxidations with the lyophilisate of Pleurotus sapidus

  摘要：

  The edible fungus Pleurotus sapidus (PSA) is a particularly interesting biocatalytic system for allylic oxidation and has a remarkably broad substrate range from terpenoids to fatty acids. The oxidations are most likely catalyzed by a lipoxygenase and involve the formation of peroxides via radical intermediates in the first rate-limiting step. We provide herein a rationalization of the observed regioselectivity of these conversions by means of computational determination of bond dissociation enthalpies of a set of tailor-made spirocyclic terpenoids. It was found that only strongly activated allylic positions (BDH298 of <80 kcal/mol) with neighboring heteroatoms or with activating alkyl groups are oxidized to the corresponding unsaturated lactones or enones, respectively. With the synthesis and purification of allylic hydroperoxide intermediates, we have been able to characterize the putative direct precursors of enones in PSA oxidations. Our results suggest a two-step oxidation mechanism involving hydroperoxide intermediates which are rapidly converted to the observed enones by an enzymatic reaction. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2015.07.008
• 作为产物：
  描述：

  (R)-4-(2,6,6-trimethylcyclohex-1-enyl)butan-2-yl acetate 在 selenium(IV) oxide 、 potassium hydroxide 作用下， 以 1,4-二氧六环 、 甲醇 、 水 为溶剂， 反应 1.5h， 生成 cis-theaspirane 、 theaspirane B
  参考文献：
  名称：

  （2R，5S）-Theaspirane被鉴定为香蕉寄主的诱人叶片，Musa spp的香蕉象鼻虫，Cosmopolites sordidus的Kairomone。

  摘要：

  耦合气相色谱-电血管造影（GC-EAG），耦合GC-质谱（GC-MS）显示了高度吸引人的感性寄主香蕉叶片Musa spp。对香蕉象鼻虫Cosmopolites sordidus产生的主要活性成分。化学合成和耦合的对映选择性（手性）GC-EAG为（2 R，5 S）-theaspirane。在实验室行为测试中，合成化合物与天然寄主叶片材料一样具有吸引力，并为控制害虫提供了新的机会。

  DOI：

  10.1002/chem.201800315

文献信息

• Enzymatic allylic oxidations with a lyophilisate of the edible fungus Pleurotus sapidus
  作者：Aljona Rickert、Verena Krombach、Oliver Hamers、Holger Zorn、Wolfgang Maison

  DOI：10.1039/c2gc16317a

  日期：——

  Allylic oxidations belong to the most attractive synthetic transformations because they convert readily available and cheap starting materials into value-added products. In this study, we describe oxidative conversions of terpenoids and a number of related cycloalkenes with a lyophilisate of the edible fungus Pleurotus sapidus. The biocatalytic protocol is simple and the biocatalyst is readily available. The conversions of various cycloalkenes proceed cleanly in most cases to the corresponding enones. The substrate scope is remarkable and includes a number of mono- and sequiterpenes, functionalized terpenoids as well as simple cyclohexenes and benzylic substrates. Enzymatic allylic oxidations by Pleurotus sapidus are thus an excellent non-toxic alternative to metal-mediated oxidation procedures in academic labs and for industrial application in food technology, cosmetics or pharmaceutical research.

  烯丙位氧化反应属于最具吸引力的合成转化之一，因为它们能够将易于获得且廉价的起始原料转化为增值产品。在本研究中，我们描述了利用食用菌棕榈侧耳（Pleurotus sapidus）的冻干粉对萜类及其相关环烷烃进行氧化转化的过程。这种生物催化方法简单，且生物催化剂易于获得。多种环烷烃的转化大多能干净地进行到相应的烯酮。底物范围显著，包括多种单萜和倍半萜、功能化萜类，以及简单的环己烯和苄位底物。棕榈侧耳的酶促烯丙位氧化因此成为学术实验室和食品技术、化妆品或药物研究领域中工业应用的一种优秀无毒替代金属介导氧化程序的方法。
• [EN] PEST ATTRACTANT COMPOSITIONS COMPRISING THEASPIRANE<br/>[FR] COMPOSITIONS ATTIRANT LES PARASITES COMPRENANT DE LA THÉASPIRANE
  申请人：ROTHAMSTED RES LTD

  公开号：WO2018142145A1

  公开（公告）日：2018-08-09

  Described herein is a pest attractant composition comprising theaspirane or an attractive derivative, homologue, isomer or mixture of isomers thereof. Also described is use of the composition for attracting pests and a trap for catching pests comprising the composition.

  本文描述了一种虫害诱引剂组合物，包括theaspirane或其吸引性衍生物、同系物、异构体或其混合物。还描述了使用该组合物来吸引害虫以及包含该组合物的捕虫器。
• ETOH, HIDEO;NISHIYAMA, ATSUKO;KOKAWA, TOSHINORI;TAKAHASHI, NOBUAKI;INA, K+, AGR. AND BIOL. CHEM., 52,(1988) N 5, 1293-1294
  作者：ETOH, HIDEO、NISHIYAMA, ATSUKO、KOKAWA, TOSHINORI、TAKAHASHI, NOBUAKI、INA, K+

  DOI：——

  日期：——
• (2<i>R</i> ,5<i>S</i> )-Theaspirane Identified as the Kairomone for the Banana Weevil, <i>Cosmopolites sordidus,</i> from Attractive Senesced Leaves of the Host Banana, <i>Musa spp</i> .
  作者：Samson A. Abagale、Christine M. Woodcock、Antony M. Hooper、John C. Caulfield、David Withall、Keith Chamberlain、Samuel O. Acquaah、Helmut Van Emden、Haruna Braimah、John A. Pickett、Michael A. Birkett

  DOI：10.1002/chem.201800315

  日期：2018.7.2

  by highly attractive senesced host banana leaves, Musa spp., for the banana weevil, Cosmopolites sordidus, is shown by coupled gas chromatography‐electroantennography (GC‐EAG), coupled GC‐mass spectrometry (GC‐MS), chemical synthesis and coupled enantioselective (chiral) GC‐EAG to be (2R,5S)‐theaspirane. In laboratory behaviour tests, the synthetic compound is as attractive as natural host leaf material

  耦合气相色谱-电血管造影（GC-EAG），耦合GC-质谱（GC-MS）显示了高度吸引人的感性寄主香蕉叶片Musa spp。对香蕉象鼻虫Cosmopolites sordidus产生的主要活性成分。化学合成和耦合的对映选择性（手性）GC-EAG为（2 R，5 S）-theaspirane。在实验室行为测试中，合成化合物与天然寄主叶片材料一样具有吸引力，并为控制害虫提供了新的机会。
• Studies towards the synthetic applicability of biocatalytic allylic oxidations with the lyophilisate of Pleurotus sapidus
  作者：Verena Weidmann、Serge Kliewer、Marko Sick、Sergej Bycinskij、Margarethe Kleczka、Julia Rehbein、Axel G. Griesbeck、Holger Zorn、Wolfgang Maison

  DOI：10.1016/j.molcatb.2015.07.008

  日期：2015.11

  The edible fungus Pleurotus sapidus (PSA) is a particularly interesting biocatalytic system for allylic oxidation and has a remarkably broad substrate range from terpenoids to fatty acids. The oxidations are most likely catalyzed by a lipoxygenase and involve the formation of peroxides via radical intermediates in the first rate-limiting step. We provide herein a rationalization of the observed regioselectivity of these conversions by means of computational determination of bond dissociation enthalpies of a set of tailor-made spirocyclic terpenoids. It was found that only strongly activated allylic positions (BDH298 of <80 kcal/mol) with neighboring heteroatoms or with activating alkyl groups are oxidized to the corresponding unsaturated lactones or enones, respectively. With the synthesis and purification of allylic hydroperoxide intermediates, we have been able to characterize the putative direct precursors of enones in PSA oxidations. Our results suggest a two-step oxidation mechanism involving hydroperoxide intermediates which are rapidly converted to the observed enones by an enzymatic reaction. (C) 2015 Elsevier B.V. All rights reserved.