(4R,4aS,6R)-2-hydroperoxy-4,4a-dimethyl-6-(prop-1-en-2-yl)-2,3,4,4a,5,6,7,8-octahydronaphthalene | 329309-57-1

• 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: (4R,4aS,6R)-2-hydroperoxy-4,4a-dimethyl-6-(prop-1-en-2-yl)-2,3,4,4a,5,6,7,8-octahydronaphthalene
• CAS: 329309-57-1
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: VCCHBZXBQNGTMT-WMSLONTCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (4R,4aS,6R)-2-hydroperoxy-4,4a-dimethyl-6-(prop-1-en-2-yl)-2,3,4,4a,5,6,7,8-octahydronaphthalene 在 lyophilisate of Pleurotus sapidus 作用下， 以 aq. buffer 为溶剂， 反应 48.0h， 以16%的产率得到(+)-香柏酮
  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：

  巴伦西亚橘烯 在 氧气 、 反式-二叔丁基连二次硝酸酯 作用下， 以 氯仿 为溶剂， 反应 90.0h， 生成 (4R,4aS,6R)-2-hydroperoxy-4,4a-dimethyl-6-(prop-1-en-2-yl)-2,3,4,4a,5,6,7,8-octahydronaphthalene
  参考文献：
  名称：

  Davies, Alwyn G.; Davison, Ian G. E., Journal of the Chemical Society. Perkin transactions II, 1989, p. 825 - 830

  摘要：

  DOI：