1-hydroperoxy-2-oxabicyclo[4.4.0]decane | 441049-09-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 1-hydroperoxy-2-oxabicyclo[4.4.0]decane
• 英文别名: 8a-Hydroperoxy-2,3,4,4a,5,6,7,8-octahydrochromene
• CAS: 441049-09-8
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: NZISRTDYIKOPEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-hydroperoxy-2-oxabicyclo[4.4.0]decane 在 硫酸 、 丙酸 作用下， 反应 0.75h， 生成 6-oxononano-9-lactone
  参考文献：
  名称：

  摘要：

  A new method for the synthesis of n-(3-acyloxypropyl)-substituted six- to thirteen-membered alkan-n-olides was developed. The method is based on the H2SO4-catalyzed reactions of oxabicycloalkenes, obtained from 2-(3-acetoxypropyl)cycloalkanes, with H2O2 and formic or acetic acid. The method includes the subsequent transformations of oxabicycloalkenes; into bicyclic hydroperoxides, peroxy ethers, and, at the final stage, into target lactones formed in 56-71% yields. These transformations are carried as a one-pot reaction.

  DOI：

  10.1023/a:1021336031371
• 作为产物：
  描述：

  3,4,5,6,7,8-hexahydro-2H-chromene 在 甲酸 、 硫酸 、 双氧水 作用下， 反应 1.0h， 生成 1-hydroperoxy-2-oxabicyclo[4.4.0]decane
  参考文献：
  名称：

  摘要：

  A new method for the synthesis of n-(3-acyloxypropyl)-substituted six- to thirteen-membered alkan-n-olides was developed. The method is based on the H2SO4-catalyzed reactions of oxabicycloalkenes, obtained from 2-(3-acetoxypropyl)cycloalkanes, with H2O2 and formic or acetic acid. The method includes the subsequent transformations of oxabicycloalkenes; into bicyclic hydroperoxides, peroxy ethers, and, at the final stage, into target lactones formed in 56-71% yields. These transformations are carried as a one-pot reaction.

  DOI：

  10.1023/a:1021336031371

文献信息

• A rearrangement of 1-hydroperoxy-2-oxabicycloalkanes into lactones of ω-acyloxy-(ω-3)-hydroxyalkanoic acids related to the Criegee reaction
  作者：Yuri N Ogibin、Alexandre O Terent'ev、Alexandre V Kutkin、Gennady I Nikishin

  DOI：10.1016/s0040-4039(01)02368-1

  日期：2002.2

  1-Hydroperoxy-2-oxabicyclo[n.4.0]alkanes (n=3, 4, 5 and 10) on heating with formic or acetic acid containing a catalytic amount of sulfuric acid undergo a rearrangement into lactones of ω-acyloxy-(ω-3)-hydroxyalkanoic acids by a mechanism related to the Criegee reaction.

  在与含有催化量硫酸的甲酸或乙酸加热下，将1-羟过氧-2-氧杂双环[ n .4.0]烷烃（n = 3、4、5和10）进行重排，使其成为ω-酰氧基-（ω -3）-羟基链烷酸是通过与Criegee反应有关的机理而形成的。
• A cheap metal catalyzed ring expansion/cross-coupling cascade: a new route to functionalized medium-sized and macrolactones
  作者：Shuai Liu、Pengchen Ma、Lu Zhang、Shenyu Shen、Hong-Jie Miao、Le Liu、K. N. Houk、Xin-Hua Duan、Li-Na Guo

  DOI：10.1039/d2sc06157k

  日期：——

  An efficient alkoxyl radical-triggered ring expansion/cross-coupling cascade was developed under cheap metal catalysis. Through the metal-catalyzed radical relay strategy, a wide range of medium-sized lactones (9–11 membered) and macrolactones (12, 13, 15, 18, and 19-membered) were constructed in moderate to good yields, along with diverse functional groups including CN, N3, SCN, and X groups installed

  在廉价金属催化下开发了一种有效的烷氧基自由基触发的扩环/交叉偶联级联。通过金属催化的自由基中继策略，以中等至良好的产率构建了各种中型内酯（9-11元）和大环内酯（12、13、15、18和19元），以及多种同时安装的功能组包括CN、N 3、SCN和X组。密度泛函理论（DFT）计算表明，环烷基-Cu（III）物质的还原消除是交叉偶联步骤更有利的反应途径。基于实验和DFT的结果，提出了用于该串联反应的Cu( I )/Cu( II )/Cu( III )催化循环。
• Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade
  作者：Jing-Qi Tao、Shuai Liu、Tian-Yu Zhang、Hong Xin、Xu Yang、Xin-Hua Duan、Li-Na Guo

  DOI：10.1016/j.cclet.2023.109263

  日期：2024.6

  A photoinduced copper-catalyzed alkoxyl triggered C−C bond cleavage/aminocarbonylation cascade is presented. Through adjusting the structure of alkoxyl radical precursors, functionalized lactones and keto-amides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions. Notably, this protocol enables the integration of lactone fragments with many amine

  提出了光诱导铜催化烷氧基触发的 C−C 键断裂/氨基羰基化级联。通过调整烷氧基自由基前体的结构，在氧化还原中性条件下合成了具有良好收率和优异官能团耐受性的官能化内酯和酮酰胺。值得注意的是，该方案能够将内酯片段与许多胺类药物和药物片段整合。