trans 1,2-limonene epoxide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: trans 1,2-limonene epoxide
• 英文别名: (R)-limonene 1,2-epoxide；cis-Δ⁸⁽⁹⁾-p-Menthen-epoxid-(1,2)；(1S,4R,6S)-1-methyl-4-prop-1-en-2-yl-7-oxabicyclo[4.1.0]heptane
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: CCEFMUBVSUDRLG-UTLUCORTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  甜橙提取物 在 叔丁基过氧化氢 作用下， 以 癸烷 、 二氯甲烷 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  Highly enantioselective olefin epoxidation controlled by helical confined environments

  摘要：

  Helical mesoporous materials of the MCM-41 type are important materials that can be prepared by onepot synthesis procedures with a co-surfactant. A control of the characteristics at a local level is of the most important in the view of the applications of such materials. However, there are not many studies relating such features `with synthetic approaches. In this work, we prepared both helical and regular channel materials from Si-based MCM-41 type. Afterward, a bpy derivative was used as ligand to coordinate The complexes and the new materials were tested as the catalytic precursors in the epoxidation of cis-cyclooctene, styrene, 1-octene, R-(+)-limonene and trans-hex-2-en-1-ol, using tertbutylhydroperoxide (TBHP) as oxidant. Although almost all the catalysts were 100% selective toward the epoxide, the conversions were in general good. The major achievement of these catalysts is an outstanding stereocontrol of the reaction products. In addition, these catalysts were found to be very effective under several circumstances. This is certainly an important contribution for such concept and may render such materials further applications where chiral recognition is important. (C) 2013 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jcat.2013.08.032

文献信息

• Towards a global greener process: from solvent-less synthesis of molybdenum(<scp>vi</scp>) ONO Schiff base complexes to catalyzed olefin epoxidation under organic-solvent-free conditions
  作者：Marina Cindrić、Gordana Pavlović、Robert Katava、Dominique Agustin

  DOI：10.1039/c6nj03174a

  日期：——

  characterised by means of IR spectroscopy, thermal analyses and also by powder and five molybdenum complexes by single crystal X-ray diffraction. The crystal structure analysis of mononuclear complexes reveal distorted octahedral Mo(VI) coordination by ONO donor atoms from a dianionic tridentate Schiff base ligand, two oxido oxygen atoms from the MoO22+ moiety and an oxygen atom from the MeOH molecule trans

  源自邻羟基醛（2-羟基苯甲醛，2-羟基-3-甲氧基苯甲醛，2-羟基-1-萘醛）和九种相应的二氧钼（VI）配合物的九个席夫碱配体，顺式-[MoO 2 L（CH 3 OH） ]或顺式-[MoO 2 L（CH 3 OH）]·CH 3 OH和双核[MoO 2 L] 2使用常规的基于溶液的方法以及机械化学方法，通过液体辅助研磨（LAG）制备了。所有产品的特征均在于红外光谱，热分析以及粉末和五种钼配合物的单晶X射线衍射。单核复合物的晶体结构分析灵兽扭曲的八面体的Mo（VI）通过从双阴离子三齿席夫碱配体ONO供电子原子，从的MoO 2的可氧化的氧原子配位2 2+部分和从MeOH中的氧原子分子的反式的氧桥氧原子。由于反式氧氧原子的作用，Mo-O（MeOH）是Mo配位球内最长的键距，它有望成为配合物最大反应性的点。已经使用叔丁基过氧化物水溶液（TBHP）作为氧化剂并且在没有有机溶剂的情况下，研究了所有络合物
• Exploring the substrate specificity of Cytochrome P450cin
  作者：Jeanette E. Stok、Peter D. Giang、Siew Hoon Wong、James J. De Voss

  DOI：10.1016/j.abb.2019.07.025

  日期：2019.9

  Initial screening indicated that P450cin could catalyse the oxidation of most of the monoterpenes tested; however, sesquiterpenes were not substrates for this enzyme or the N242A mutant. Additionally, both P450cin mutants were found to be able to oxidise other bicyclic monoterpenes. For example, the oxidation of (R)- and (S)-camphor by N242T favoured the production of 5-endo-hydroxycamphor (65-77% of the

  细胞色素P450是催化多种化合物氧化的酶，这些化合物从较小的挥发性化合物（如单萜）到较大的化合物（如类固醇）不等。可以对这些酶进行修饰，以选择性地氧化感兴趣的底物，从而使其在生物技术工业中的应用具有吸引力。在这项研究中，我们筛选了一个针对P450cin和两个P450cin突变体N242A和N242T的萜烯和类萜化合物的小文库，先前已证明它们会影响选择性。初步筛选表明，P450cin可以催化大多数测试的单萜的氧化。然而，倍半萜烯不是该酶或N242A突变体的底物。另外，发现两个P450cin突变体都能够氧化其他双环单萜。例如，N242T对（R）和（S）樟脑的氧化作用有利于生成5-内羟基樟脑（总产物的65-77％，取决于对映异构体），这与以前对（R ）-用N242A（73％）制成的樟脑。还观察到（R）-和（S）-柠檬烯的选择性，其中N242A主要产生顺式-柠檬烯1,2-环氧化物（（R）-柠檬烯氧
• Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2
  作者：A. Simaioforidou、M. Papastergiou、A. Margellou、D. Petrakis、M. Louloudi

  DOI：10.1016/j.molcata.2016.08.033

  日期：2017.1

  Two types of heterogeneous catalytic materials, Mn-II-L(3)imid@Cox and Mn-II-L(3)imid@PCox, have been synthesized and compared by covalent grafting of a catalytically active [Mn-II-L(3)imid] complex on the surface of an oxidized activated carbon (Cox) and an oxidized pyrolytic carbon from recycled-tire char (PCox). Both hybrids are non-porous bearing graphitic layers intermixed with disordered sp(2)/sp(3) carbon units. Raman spectra show that (I-D/I-G)(activatedcarbon) > (I-D/I-G)(pyrolyticcarbon) revealing that oxidized activated carbon(Cox) is less graphitized than oxidized pyrolytic carbon (PCox). The Mn-II-L(3)imid@Cox and Mn-II-L(3)imid@PCox catalysts were evaluated for alkene oxidation with H2O2 in the presence of CH3COONH4. Both showed high selectivity towards epoxides and comparing the achieved yields and TONs, they appear equivalent. However, Mn-II-L(3)imid@PCox catalyst is kinetically faster than the Mn-II-L(3)imid@Cox (accomplishing the catalytic runs in 1.5 h vs. 5 h). Thus, despite the similarity in TONs Mn-II-L(3)imid@PCox achieved extremely higher TOFs vs. Mn-II-L(3)imid@Cox. Intriguingly, in terms of recyclability, Mn-II-L(3)imid@Cox could be reused for a 2th run showing a similar to 20% loss of its catalytic activity, while Mn-II-L(3)imid@PCox practically no recyclable. This phenomenon is discussed in a mechanistic context; interlinking oxidative destruction of the Mn-complex with high TOF5 for Mn-II-L(3)imid@PCox, while the low-TOFs of Mn-II-L(3)imid@Cox are preventive for the oxidative destruction of the Mn-complex. (C) 2016 Elsevier B.V. All rights reserved.
• Highly enantioselective olefin epoxidation controlled by helical confined environments
  作者：Cristina I. Fernandes、Marta S. Saraiva、Teresa G. Nunes、Pedro D. Vaz、Carla D. Nunes

  DOI：10.1016/j.jcat.2013.08.032

  日期：2014.1

  Helical mesoporous materials of the MCM-41 type are important materials that can be prepared by onepot synthesis procedures with a co-surfactant. A control of the characteristics at a local level is of the most important in the view of the applications of such materials. However, there are not many studies relating such features `with synthetic approaches. In this work, we prepared both helical and regular channel materials from Si-based MCM-41 type. Afterward, a bpy derivative was used as ligand to coordinate The complexes and the new materials were tested as the catalytic precursors in the epoxidation of cis-cyclooctene, styrene, 1-octene, R-(+)-limonene and trans-hex-2-en-1-ol, using tertbutylhydroperoxide (TBHP) as oxidant. Although almost all the catalysts were 100% selective toward the epoxide, the conversions were in general good. The major achievement of these catalysts is an outstanding stereocontrol of the reaction products. In addition, these catalysts were found to be very effective under several circumstances. This is certainly an important contribution for such concept and may render such materials further applications where chiral recognition is important. (C) 2013 Elsevier Inc. All rights reserved.