theaspirane | 153153-55-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: theaspirane
• 英文别名: (2R,5R)-2,6,6,10-tetramethyl-1-oxaspiro[4.5]dec-9-en-8-one
• CAS: 153153-55-0
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: AXQMCYYCOKLZPP-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  cis-theaspirane 在 lyophilisate of Pleurotus sapidus 、 air 作用下， 以 aq. buffer 为溶剂， 反应 72.0h， 生成 theaspirane
  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

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。
• 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.