(4R,8R)-8,9-epoxy-p-menth-1-ene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (4R,8R)-8,9-epoxy-p-menth-1-ene
• 英文别名: (2R)-2-methyl-2-[(1R)-4-methylcyclohex-3-en-1-yl]oxirane
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: PJGRMBOWSWHGDV-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 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

• 作为反应物：
  描述：

  (4R,8R)-8,9-epoxy-p-menth-1-ene 在 四甲基氢氧化铵 、 二甲基亚砜 作用下， 反应 48.0h， 生成 (4R,8R,4'R,8'R)-9,9'-oxybis(p-menth-1-en-8-ol)
  参考文献：
  名称：

  Carman, Raymond M.; Voss, James J. De; Greenfield, Kay L., Australian Journal of Chemistry, 1986, vol. 39, # 3, p. 441 - 446

  摘要：

  DOI：
• 作为产物：
  描述：

  (4R,8R)-8-hydroxy-p-menth-1-en-9-yl p-toluenesulfonate 在 potassium carbonate 作用下， 以 乙醚 为溶剂， 反应 120.0h， 以70%的产率得到(4R,8R)-8,9-epoxy-p-menth-1-ene
  参考文献：
  名称：

  Carman, Raymond M.; Voss, James J. De; Greenfield, Kay L., Australian Journal of Chemistry, 1986, vol. 39, # 3, p. 441 - 446

  摘要：

  DOI：

文献信息

• Efficient Epoxidation of Electron-Deficient Alkenes with Hydrogen Peroxide Catalyzed by [γ-PW10O38V2(μ-OH)2]3−
  作者：Keigo Kamata、Kosei Sugahara、Kazuhiro Yonehara、Ryo Ishimoto、Noritaka Mizuno

  DOI：10.1002/chem.201101001

  日期：2011.6.27

  epoxidized without formation of the corresponding amides. In addition, I could rapidly (≤10 min) catalyze epoxidation of various kinds of terminal, internal, and cyclic alkenes with H2O2 under the stoichiometric conditions. The mechanistic, spectroscopic, and kinetic studies showed that the I‐catalyzed epoxidation consists of the following three steps: 1) The reaction of I with H2O2 leads to reversible formation

  甲二钒取代的磷钨，[γ-PW 10 ö 38 V 2（μ-OH）2 ] 3-（我），显示出最高的催化活性对H 2 ö 2中钒和钨络合物的乙酸烯丙酯的环氧化的基于营业额为210。在存在I的情况下，烯丙基位置带有乙酸盐，醚，羰基和氯基的各种缺电子烯烃可以高收率将其化学等价地氧化成相应的环氧化物，而等摩尔量的H 2 O 2关于基板。甚至丙烯腈和甲基丙烯腈也可以被环氧化而不形成相应的酰胺。另外，在化学计量比下，我可以快速（≤10分钟）用H 2 O 2催化各种末端，内部和环状烯烃的环氧化。的机理，光谱学，和动力学研究表明，我催化的环氧化反应由以下三个步骤组成：1）的反应我用H 2 ö 2所导致可逆形成一个氢过物种的[γ-PW 10 ö 38 V 2（μ-OH）（μ-OOH）] 3−（II），2）的连续脱水II形式的活性氧种与过氧组[γ-PW 10 ö 38 V 2（μ-η 2：η 2 -O 2）]
• Chiral Cationic [Cp′Mo(CO) ₂ (NCMe)] ⁺ Species – Catalyst Precursors for Olefin Epoxidation with H ₂ O ₂ and <i>tert</i> ‐Butyl Hydroperoxide
  作者：Patrícia M. Reis、Carla A. Gamelas、José A. Brito、Nathalie Saffon、Montserrat Gómez、Beatriz Royo

  DOI：10.1002/ejic.201001065

  日期：2011.2

  coordination to molybdenum and tungsten afforded optically pure (R)-CpoxM(η3-C3H5)(CO)2 (M = Mo, W) in which the pendant oxazoline fragment is not coordinated to the metal center. Reaction of (R)-CpoxMo(η3-C3H5)(CO)2 with tetrafluoroboric acid gives the bidentate η5-cyclopentadienyloxazoline complex [CpoxMo(CO)2(NCMe)]BF4 in which the oxazoline is coordinated through the N-atom to the molybdenum center. Their

  已经制备了带有手性恶唑啉侧基（Cpox）的新型环戊二烯基配体。它与钼和钨的配位提供了光学纯的 (R)-CpoxM(η3-C3H5)(CO)2 (M = Mo, W)，其中悬垂的恶唑啉片段未与金属中心配位。(R)-CpoxMo(η3-C3H5)(CO)2 与四氟硼酸反应得到二齿 η5-环戊二烯恶唑啉配合物 [CpoxMo(CO)2(NCMe)]BF4，其中恶唑啉通过 N 原子配位到钼中心。研究了它们在 H2O2 和叔丁基过氧化氢 (TBHP) 作为氧化剂的顺式环辛烯、(R)-柠檬烯和反式-β-甲基苯乙烯的环氧化反应中的催化性能。(R)-CpoxW(η3-C3H5)(CO)2 显示出高催化活性，可在 2 小时内用 H2O2 实现环辛烯环氧化物的定量转化。[CpoxMo(CO)2(NCMe)]+ 已被证明是一种有效的 TBHP 和 H2O2 催化剂，分别在 30 分钟和 11 小时内实现了相应环
• Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes
  作者：Katarzyna A. Maltby、Marc Hutchby、Pawel Plucinski、Matthew G. Davidson、Ulrich Hintermair

  DOI：10.1002/chem.201905561

  日期：2020.6.10

  without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double‐activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by‐product formation in commercial mixtures of 1,2‐limomene oxide. Carbonation of 8,9‐limonene epoxide furnished the 8,9‐limonene

  据报道，柠檬烯衍生的单官能环状碳酸酯的选择性催化合成及其随后通过硫醇-烯加成和胺开环进行的官能化。在环碳酸酯合成中，用于柠檬烯环氧化的磷钨酸多金属氧酸盐催化剂也显示出活性，可进行环状碳酸酯合成，无需间歇性环氧化物分离即可进行两步一锅合成。当与经典的卤化物催化剂结合使用时，多金属氧酸盐通过两种底物的协同双重活化提高了碳酸化速率。该顺异构体被证明是造成1,2-氧化亚胺氧化物商业混合物中不完全转化和副产物形成的原因。8,9-柠檬烯环氧化物的碳酸化首次提供了8,9-柠檬烯碳酸酯。两种环状碳酸酯均进行硫醇-烯加成反应，生成连接的二一碳酸酯，可用于线性非异氰酸酯聚氨酯的合成，如其与N-己基胺的开环简便所示。因此，对于单官能碳酸柠檬烯的选择性催化途径使新型生物基聚合物可以直接进入单体。
• Trifluoromethyl Ketone Galactose Catalyst for Asymmetric Epoxidation: Experimental and Theoretical Model
  作者：Daniela Imperio、Emanuele Casali、Erika Del Grosso、Diego Caprioglio、Alberto Minassi、Luigi Panza

  DOI：10.1002/ejoc.202301163

  日期：2024.2.12

  A novel organocatalyst based on a d-galactose skeleton is obtained by inserting a trifluoromethyl ketone on C6. It forms in situ, in the presence of Oxone, a dioxirane able to perform the asymmetric epoxidation of olefins. A theoretical study and a mnemonic model to predict the stereochemical results are elaborated.

  通过在 C6 上插入三氟甲基酮获得基于d-半乳糖骨架的新型有机催化剂。它在 Oxone 存在下原位形成能够进行烯烃不对称环氧化的二环氧乙烷。阐述了预测立体化学结果的理论研究和助记模型。
• Design, Preparation, and Study of Catalytic Gated Baskets
  作者：Bao-Yu Wang、Teodora Žujović、Daniel A. Turner、Christopher M. Hadad、Jovica D. Badjić

  DOI：10.1021/jo202443j

  日期：2012.3.16

  We report a diastereoselective synthetic method to obtain a family catalytic molecular baskets containing a spacious cavity (similar to 570 angstrom(3)). These supramolecular catalysts were envisioned, via the process of gating, to control the access of substrates to the embedded catalytic center and thereby modulate the outcome of chemical reactions. In particular, gated basket 1 comprises a porphyrin "floor" fused to four phthalimide "side walls" each carrying a revolving aromatic "gate". With the assistance of H-1 NMR and UV-vis spectroscopy, we demonstrated that the small 1-methylimidazole guest (12, 94 angstrom(3)) would coordinate to the interior while the large' 1,5-diadamantylimidazole guest (14, 361 angstrom(3)) is relegated to tilt: exterior of basket Zn(II)-1. Subsequently, we examined the epoxidation of differently sized and shaped alkenes 18-21 with catalytic baskets 12(in)-Mn(III)-1 and 14(out)- Mn(III)-1 in the presence of the sacrificial oxidant iodosylarene. The epoxidation of cis-stilbene occurred in the cavity of 14(out)-, Mn(III)-1 and at the outer face of 12(in)Mn(III)-1 with the stereoselectivity of the two transformations being somewhat different. Importantly, catalytic basket 14(out)-Mn(III)-1 was capable of kinetically resolving an equimolar mixture of cis-2-octene 20 and cis-cyclooctene 21 via promotion of the transformation in its cavity.