1-oxaspiro[5.5]undec-3-ene | 7160-77-2

• 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-ene
• CAS: 7160-77-2
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: JIIDPKMBTFQSFR-UHFFFAOYSA-N

物化性质

• 沸点：
  230.4±29.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  1-oxaspiro[5.5]undec-3-ene 在 lyophilisate of Pleurotus sapidus 、 air 作用下， 以 aq. buffer 为溶剂， 反应 72.0h， 以11%的产率得到1-oxaspiro[5,5]undec-3-en-2-one
  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：

  亚甲基环己烷氧化物 在 4,4'-di(tert-butyl)-[1,1-biphenyl]yllithium 、 甲基磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 1-oxaspiro[5.5]undec-3-ene
  参考文献：
  名称：

  Synthetically useful .beta.-lithioalkoxides from reductive lithiation of epoxides by aromatic radical anions

  摘要：

  DOI：

  10.1021/jo00292a029

文献信息

• Synthesis of Spiro Ethers by Ring Closing Metathesis
  作者：Martin E. Maier、Michael Bugl

  DOI：10.1055/s-1998-1943

  日期：1998.12

  Starting from the cyclic ketones 1 a - d, the dienes 3 a - e were prepared. The ring closing metathesis reaction of these dienes using the Grubbs catalyst 5 provided the corresponding spiro ethers 4 a - e in good yield. Force field calculations indicate that the conformer with the oxygen in axial position is favored.

  从环酮 1 a - d 开始，制备二烯 3 a - e。使用格拉布斯催化剂 5 对这些二烯进行闭环偏析反应，可以得到相应的螺醚 4 a - e，收率很高。力场计算表明，氧处于轴向位置的构象更受青睐。
• On the choice of Lewis acids for the Prins reaction; two total syntheses of (±)-Civet
  作者：Freda K. Chio、Julie Warne、Damien Gough、Mark Penny、Sasa Green (née Martinović)、Simon J. Coles、Mike B. Hursthouse、Peter Jones、Lorraine Hassall、Thomas M. McGuire、Adrian P. Dobbs

  DOI：10.1016/j.tet.2011.05.019

  日期：2011.7

  While developing new variations of the Prins cyclisation reaction, the effect of the choice of Lewis acid on the outcome of the reaction and the product(s) has been investigated, yielding hitherto unseen dihydropyran products in the Prins cyclisation reaction of homoallylic alcohols, and two new modifications of the reaction: the triflate-trapped Prins adduct and the Mukaiyama-Aldol-silyl-Prins reaction. Two of these methods are employed in two complementary total syntheses of the important perfumery compound, (+/-)-Civet. (C) 2011 Elsevier Ltd. All rights reserved.
• COHEN, THEODORE;JEONG, IN-HOWA;MUDRYK, BOGUSLAW;BHUPATHY, M.;AWAD, MOHAME+, J. ORG. CHEM., 55,(1990) N, C. 1528-1536
  作者：COHEN, THEODORE、JEONG, IN-HOWA、MUDRYK, BOGUSLAW、BHUPATHY, M.、AWAD, MOHAME+

  DOI：——

  日期：——
• Synthetically useful .beta.-lithioalkoxides from reductive lithiation of epoxides by aromatic radical anions
  作者：Theodore Cohen、In Howa Jeong、Boguslaw Mudryk、M. Bhupathy、Mohamed M. A. Awad

  DOI：10.1021/jo00292a029

  日期：1990.3
• 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.