(1S,3S)-6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-yl hydroperoxide | 265111-28-2

• 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: (1S,3S)-6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-yl hydroperoxide
• 英文别名: (1R,5R)-3-hydroperoxy-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptane；(1R,3S,5R)-3-hydroperoxy-6,6-dimethyl-2-methylidenebicyclo[3.1.1]heptane
• CAS: 265111-28-2
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: UQHVOBUXTHVSBI-VGMNWLOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,3S)-6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-yl hydroperoxide 在 titanium(IV) isopropylate 、 草酰氯 、 三氟化硼乙醚 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.25h， 生成 (5R)-2-hydroxymethyl-5-isopropenyl-cyclohex-2-enone
  参考文献：
  名称：

  的简便3步合成（- [R ）- 7 - Hydroxycarvone从（小号）-α-蒎烯

  摘要：

  的一种方便的3步合成（- [R ）- 7 - hydroxycarvone（2）已被开发从（起始小号）-α蒎烯（7），光氧化使用，氧化和断裂反应。还描述了环氧醇6的改进合成和不寻常的Ti（OiPr）4催化的羟基环氧化物对酮醇的重排。

  DOI：

  10.1021/jo050217h
• 作为产物：
  描述：

  (-)-α-蒎烯 在 氧气 、 tetraphenylporphyrin 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (1S,3S)-6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-yl hydroperoxide
  参考文献：
  名称：

  的简便3步合成（- [R ）- 7 - Hydroxycarvone从（小号）-α-蒎烯

  摘要：

  的一种方便的3步合成（- [R ）- 7 - hydroxycarvone（2）已被开发从（起始小号）-α蒎烯（7），光氧化使用，氧化和断裂反应。还描述了环氧醇6的改进合成和不寻常的Ti（OiPr）4催化的羟基环氧化物对酮醇的重排。

  DOI：

  10.1021/jo050217h

文献信息

• Selective C–H Allylic Oxygenation of Cycloalkenes and Terpenoids Photosensitized by [Cu(Xantphos)(neoc)]BF₄
  作者：Michael G. Kallitsakis、Dimitra K. Gioftsidou、Marina A. Tzani、Panagiotis A. Angaridis、Michael A. Terzidis、Ioannis N. Lykakis

  DOI：10.1021/acs.joc.1c01591

  日期：2021.10.1

  We present herein for the first time the use of the [Cu(Xantphos)(neoc)]BF4 as a photocatalyst for the selective C–H allylic oxygenation of cycloalkenes into the corresponding allylic hydroperoxides or alcohols in the presence of molecular oxygen. The proposed methodology affords the products at good yields and has also been applied successfully to several bioactive terpenoids, such as geraniol, linalool

  我们在此首次提出使用 [Cu(Xantphos)(neoc)]BF 4作为光催化剂，在分子氧存在下将环烯烃选择性 C-H 烯丙基氧化成相应的烯丙基氢过氧化物或醇。所提出的方法以良好的产量提供了产品，并且还成功地应用于几种生物活性萜类化合物，如香叶醇、芳樟醇、β-香茅醇和植醇。一项还涉及动力学同位素效应 (KIE) 的机械研究支持所提出的单线态氧介导的反应。基于观察到的高化学选择性和产率以及快速和清洁的反应过程，本催化体系 [Cu(Xantphos)(neoc)]BF 4也已应用于实验室规模的合成顺式玫瑰氧化物，一种众所周知的香料成分，用于玫瑰和天竺葵香水。
• “Dark” Singlet Oxygen Made Easy
  作者：Mohamed Elsherbini、Rudolf K. Allemann、Thomas Wirth

  DOI：10.1002/chem.201903505

  日期：2019.9.25

  An operationally simple continuous flow generator of "dark" singlet oxygen has been developed. The singlet oxygen was efficiently reacted with several chemical traps to give the corresponding oxygenated products in high yields. The developed "dark" singlet oxygen generator has been successfully applied in the synthesis of the antimalarial drug artemisinin.

  已经开发了一种操作简单的“深色”单重态氧的连续流发生器。单线态氧与几个化学捕集阱有效反应，以高收率得到相应的氧化产物。研发的“深色”单线态氧气发生器已成功用于抗疟药青蒿素的合成。
• Highly Efficient Continuous Flow Reactions Using Singlet Oxygen as a “Green” Reagent
  作者：François Lévesque、Peter H. Seeberger

  DOI：10.1021/ol2017643

  日期：2011.10.7

  Described is a new method for the efficient in situ production of singlet oxygen in a simple continuous flow photochemical reactor. The extremely large interfacial area generated by running the biphasic mixture in a narrow channel at a high flow rate ensures high throughput as well as fast and efficient oxidation of various alkenes, 1,3-dienes, and thioethers on a preparative scale.

  描述了一种在简单连续流光化学反应器中有效原位生产单重态氧的新方法。通过在狭窄通道中以高流速运行双相混合物而产生的极大的界面面积可确保高通量以及制备规模上各种烯烃，1,3-二烯和硫醚的快速有效氧化。
• Improved synthesis of (R)-7-hydroxycarvone from (S)-α-pinene
  作者：Yuki Egoshi、Ryosuke Kondo、Yukiko Yoshimoto、Toru Sugiyama、Toyonobu Usuki

  DOI：10.1016/j.tetlet.2013.10.066

  日期：2013.12

  natural products, is described. Optimization of the reaction conditions for photooxygenation and migration of (S)-α-pinene 2, tetrapropylammonium perruthenate (TPAP) oxidation of the generated alcohol, and a subsequent ring-opening reaction in the presence of Cu(OTf)2 led to the synthesis of 1 with good reproducibility. The desired product 1 was thus obtained in 46% yield over three steps.

  描述了三步合成（R）-7-羟基香芹酮（1）的方法，该方法有望成为通用制备天然产物的重要组成部分。（S）-α-pine烯2的光氧合和迁移反应条件的优化，生成的醇的四丙基过钌酸铵（TPAP）氧化以及随后在Cu（OTf）2存在下的开环反应导致合成的1，重现性好。因此，在三个步骤中以46％的产率获得了所需的产物1。
• Photooxidation of Olefins under Oxygen in Platinum(II) Complex-Loaded Mesoporous Molecular Sieves
  作者：Ke Feng、Ren-Yuan Zhang、Li-Zhu Wu、Bo Tu、Ming-Li Peng、Li-Ping Zhang、Dongyuan Zhao、Chen-Ho Tung

  DOI：10.1021/ja0648256

  日期：2006.11.1

  Cyclometalated platinum(II) complex has been successfully incorporated into the (3-aminopropyl) triethoxysilane-modified channels of ordered mesoporous silica SBA-15 that has large pore hexagonal channels. Studies on the O-1(2) generation conclusively demonstrates that the olefins in the nano-channels of SBA-15 can be enriched 8 times higher than those in the homogeneous solution as the diffusion quantum yield of singlet oxygen (O-1(2)) is assumed to be unit. The platinum( II) complex loaded in the channel of SBA-15 is stable, and the photosensitized oxidation occurs efficiently. No obvious degradation and leaching of photosensitizers is observed even after 10 runs. Only a simple filtration is needed for the recycled use of the expensive noble metal catalysts. This versatile system is a good example of photochemical reactions occurring in the mesoporous silica molecular sieve. SBA-15 not only provides a support for the photosensitizer, but also acts as a nano-reactor to facilitate the photooxidation.