(+)-(1'R,2'R,3'S)-4-(2',3'-Epoxy-2',6',6'-trimethylcyclohex-1'-yl)but-3-en-2-on | 108944-32-7

• 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: (+)-(1'R,2'R,3'S)-4-(2',3'-Epoxy-2',6',6'-trimethylcyclohex-1'-yl)but-3-en-2-on
• 英文别名: (3E)-4-[(1R,2R,6S)-1,3,3-Trimethyl-7-oxabicyclo[4.1.0]hept-2-yl]-3-buten-2-one；(E)-4-[(1R,2R,6S)-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptan-2-yl]but-3-en-2-one
• CAS: 108944-32-7
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: ODMUHAHUBCUABS-AJKHXVQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(1'R,2'R,3'S)-4-(2',3'-Epoxy-2',6',6'-trimethylcyclohex-1'-yl)but-3-en-2-on 在 硫酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 0.25h， 以65.41%的产率得到(rac)-(E)-4-((syn,anti)-2,3-dihydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one
  参考文献：
  名称：

  光学活性4,5-环氧-4,5-二氢-α-紫罗兰酮和立体异构体合成4,5：4'，5'-Diepoxy-4,5,4'，5'-tetrahydro-ϵ，ϵ-carotine顺式和反式Verlauf ihrer水解酶

  摘要：

  旋光的4,5-环氧-4,5-二氢-α-紫罗兰酮; 立体异构体4,5：4'，5'-Diepoxy-4,5,4'，5'-tetrahydro-ϵ，ϵ-carotenes的合成及其水解的立体过程

  DOI：

  10.1002/hlca.19860690409
• 作为产物：
  描述：

  [R-(E)]-4-(2,6,6-三甲基-2-环己烯-1-基)-3-丁烯-2-酮 在 三氟过氧乙酸 、 sodium carbonate 作用下， 以 二氯甲烷 为溶剂， 生成 (rac)-4-(2,3-epoxy-2,6,6-trimethylcyclohexyl)-3-buten-2-one 、 (+)-(1'R,2'R,3'S)-4-(2',3'-Epoxy-2',6',6'-trimethylcyclohex-1'-yl)but-3-en-2-on
  参考文献：
  名称：

  Diastereoface-Selective Epoxidations: Dependency on the Reagent Electrophilicity

  摘要：

  Substrate-imposed steric constraints can be overriden by the pronounced preference of strong peracids for epoxidation on the π face, which has the highest electron density. For example, the syn:anti ratio for reaction (1) with CF3 CO3 H in CH2 Cl2 is 82:18, that with CH3 CO3 H in toluene is 3:97.

  DOI：

  10.1002/(sici)1521-3773(19980918)37:17<2407::aid-anie2407>3.0.co;2-w

文献信息

• Total Synthesis of (+)-Granatumine A and Related Bislactone Limonoid Alkaloids via a Pyran to Pyridine Interconversion
  作者：Alexander W. Schuppe、Yizhou Zhao、Yannan Liu、Timothy R. Newhouse

  DOI：10.1021/jacs.9b04508

  日期：2019.6.12

  We report the first total synthesis of (+)-granatumine A, a limonoid alkaloid with PTP1B inhibitory activity, in ten steps. Over the course of this study, two key methodological advances were made: a cost-effective procedure for ketone α,β-dehydrogenation using allyl-Pd catalysis, and a Pd-catalyzed protocol to convert epoxyketones to 1,3-diketones. The central tetrasubstituted pyridine is formed by

  我们报告了 (+)-granatumine A 的第一个全合成，这是一种具有 PTP1B 抑制活性的柠檬苦素生物碱，分十个步骤。在这项研究的过程中，取得了两个关键的方法学进展：使用烯丙基钯催化的酮 α,β-脱氢的成本效益程序，以及将环氧酮转化为 1,3-二酮的钯催化方案。中心的四取代吡啶由收敛的 Knoevenagel 缩合和羰基选择性电环化级联反应形成，然后将 2 H-吡喃直接转化为吡啶。这些研究导致了这个家族的两个成员的结构修正。
• Lipase-mediated synthesis of the enantiomeric forms of 4,5-epoxy-4,5-dihydro-α-ionone and 5,6-epoxy-5,6-dihydro-β-ionone. A new direct access to enantiopure (R)- and (S )-α-ionone
  作者：Josefina Aleu、Elisabetta Brenna、Claudio Fuganti、Stefano Serra

  DOI：10.1039/a808780f

  日期：——

  Stereoselective lipase-mediated esterifications of epoxy-α-ionol 5 and epoxy-β-ionol 9 afforded suitable precursors of the enantiomers of the corresponding oxidised derivatives epoxy-α-ionone 3 and epoxy-β-ionone 4. An interesting development of this work is the easy conversion of enantiopure 3a and 3b into highly valuable enantiopure (S)- and (R)-ionone (1a and 1b) via a mild deoxygenation reaction.

  脂肪酶介导的环氧-δ-酮 5 和环氧-δ-酮 9 的立体选择性酯化反应得到了相应氧化衍生物环氧-δ-酮 3 和环氧-δ-酮 4 对映体的合适前体。这项工作的一个有趣进展是，通过温和的脱氧反应，对映体纯品 3a 和 3b 很容易转化为高价值的对映体纯品 (S)- 和 (R)-ionone (1a 和 1b)。
• Oxidation of alkenes with non-heme iron complexes: suitability as an organic synthetic method
  作者：David Clemente-Tejeda、Francisco A. Bermejo

  DOI：10.1016/j.tet.2014.10.037

  日期：2014.12

  In the course of a preliminary study to determine the preparative value and the synthetic applications of the non-heme iron(II) complexes Fe(bpmen)(OTf)(2) and Fe(tpa)(OTf)(2), in particular the oxidation of alkenes by using hydrogen peroxide as the terminal oxidant, we have found significant differences in catalyst behavior. After several attempts it was clear that the preparative relevance of the oxidation processes was linked to the concentration of the catalyst and optimal results were obtained when the concentration value was 5 mol %. At that concentration, the Fe(bpmen)(OTf)(2) catalyst mostly gave rise to mixtures of the epoxide and the trans-dihydroxylation products formed by water-assisted hydrolytic cleavage of the epoxides. Furthermore, the use of the tripodal ligand tpa led to cis dihydroxylation products. When deactivated olefins were used as substrates for the oxidation reaction, the cis-diols were obtained exclusively, although with modest conversions, regardless of the catalyst used. (C) 2014 Elsevier Ltd. All rights reserved.
• Optisch aktive 4,5-Epoxy-4,5-dihydro-?-ionone und Synthese der stereoisomeren 4,5:4?,5?-Diepoxy-4,5,4?,5?-tetrahydro-?,?-carotine und der sterische Verlauf ihrer Hydrolyse
  作者：Peter Uebelhart、Andreas Baumeler、Andreas Haag、Roland Prewo、Jost Hans Bieri、Conrad Hans Eugster

  DOI：10.1002/hlca.19860690409

  日期：1986.6.18

  Optically Active 4,5-Epoxy-4,5-dihydro-α-ionones; Synthesis of the Stereoisomeric 4,5:4′,5′-Diepoxy-4,5,4′,5′-tetrahydro-ϵ,ϵ-carotenes and the Steric Course of their Hydrolysis

  旋光的4,5-环氧-4,5-二氢-α-紫罗兰酮; 立体异构体4,5：4'，5'-Diepoxy-4,5,4'，5'-tetrahydro-ϵ，ϵ-carotenes的合成及其水解的立体过程
• Diastereoface-Selective Epoxidations: Dependency on the Reagent Electrophilicity
  作者：Charles Fehr

  DOI：10.1002/(sici)1521-3773(19980918)37:17<2407::aid-anie2407>3.0.co;2-w

  日期：1998.9.18

  Substrate-imposed steric constraints can be overriden by the pronounced preference of strong peracids for epoxidation on the π face, which has the highest electron density. For example, the syn:anti ratio for reaction (1) with CF3 CO3 H in CH2 Cl2 is 82:18, that with CH3 CO3 H in toluene is 3:97.