1-oxaspiro[5,5]undec-3-en-2-one | 118512-57-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 1-oxaspiro[5,5]undec-3-en-2-one
• 英文别名: 1-Oxaspiro[5.5]undec-3-en-2-one
• CAS: 118512-57-5
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: CLNVVGRCERCTEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  1-烯丙基环己醇 在 Grubbs catalyst first generation 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 1-oxaspiro[5,5]undec-3-en-2-one
  参考文献：
  名称：

  融合易位和光化学Csp 3 -H活化：获得掩盖的β-甲酰基己醇化物及其重排为呋喃呋喃酮

  摘要：

  β-掩蔽的甲酰基己醇化物是通过三步顺序制备的，包括均丙醇的酯化，闭环易位和光化学诱导的二恶烷基的加成。当在氧化条件下处理时，加合物经历了缩酮基团的裂解，重新排列为母体呋喃酮，在某些生物活性化合物中发现了这种结构。

  DOI：

  10.1016/j.tet.2018.06.040

文献信息

• Gold-Catalyzed Intermolecular Reactions of Propiolic Acids with Alkenes: [4 + 2] Annulation and Enyne Cross Metathesis
  作者：Hyun-Suk Yeom、Jaeyoung Koo、Hyun-Sub Park、Yi Wang、Yong Liang、Zhi-Xiang Yu、Seunghoon Shin

  DOI：10.1021/ja210792e

  日期：2012.1.11

  A gold-catalyzed intermolecular reaction of propiolic acids with alkenes led to a [4 + 2] annulation or enyne cross metathesis. The [4 + 2] annulation proceeds with net cis-addition with respect to alkenes and provides an expedient route to α,β-unsaturated δ-lactones, for which preliminary asymmetric reactions were also demonstrated. For 1,2-disubstituted alkenes, unprecedented enyne cross metathesis

  丙炔酸与烯烃的金催化分子间反应导致 [4 + 2] 环化或烯炔交叉复分解。[4 + 2] 环化与烯烃的净顺式加成一起进行，并为 α,β-不饱和 δ-内酯提供了便利的途径，也证明了初步的不对称反应。对于 1,2-二取代烯烃，前所未有的烯炔交叉复分解反应以完全立体定向的方式得到 1,3-二烯。DFT 计算和实验表明，环丁烯衍生物不是可行的中间体，协同 σ 键重排期间的空间相互作用是观察到的独特立体特异性的原因。
• A practical route towards α,β-unsaturated δ-lactones based on a [3+3] strategy. Synthesis of (−)-argentilactone
  作者：Juan Carlos Carretero、Léon Ghosez

  DOI：10.1016/s0040-4039(00)87834-x

  日期：——
• 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.