(3R,4R)-3,4-epoxy-6-methoxy-2,2-dimethylchromane | 350716-15-3

• 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: (3R,4R)-3,4-epoxy-6-methoxy-2,2-dimethylchromane
• 英文别名: (3R,4R)-6-methoxy-2,2-dimethylchromene；2,2-dimethyl-6-methyoxy-2H-chromene oxide；(3R,4R)-3,4-epoxy-2,2-dimethyl-6-methoxychromane；(3R,4R)-2,2-dimethyl-6-methoxychromene oxide；(1aR,7bR)-6-methoxy-2,2-dimethyl-1a,7b-dihydrooxireno[2,3-c]chromene
• CAS: 350716-15-3
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: DWQLEXJSAGRCJG-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  31
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4R)-3,4-epoxy-6-methoxy-2,2-dimethylchromane 在 titanium(IV) isopropylate 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以93%的产率得到(3R,4S)-3,4-dihydroxy-6-methoxy-2,2-dimethyl-chroman
  参考文献：
  名称：

  The first asymmetric total synthesis of several 3,4-dihydroxy-2,2-dimethyl-chroman derivatives

  摘要：

  The stereoisomers of 3,4-dihydroxy-6-methoxy-2,2-dimethyl-chroman 1a-c and 3,4,7-trihydroxy-6-acetyl-2,2-dimethyl-chroman 2a-c were conveniently prepared for the first time via a synthesis in which Sharpless asymmetric dihydroxylation and Jacobsen's catalytic asymmetric epoxidation are the key steps. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.10.040
• 作为产物：
  描述：

  6-methoxy-2,2-dimethyl-3,4-dihydro-2H-1-benzopyran 在 sodium tetrahydroborate 、 R,R-Jacobsen's catalyst 、 对甲苯磺酸 、 N-甲基吗啉氧化物 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 (3R,4R)-3,4-epoxy-6-methoxy-2,2-dimethylchromane
  参考文献：
  名称：

  The first asymmetric total synthesis of several 3,4-dihydroxy-2,2-dimethyl-chroman derivatives

  摘要：

  The stereoisomers of 3,4-dihydroxy-6-methoxy-2,2-dimethyl-chroman 1a-c and 3,4,7-trihydroxy-6-acetyl-2,2-dimethyl-chroman 2a-c were conveniently prepared for the first time via a synthesis in which Sharpless asymmetric dihydroxylation and Jacobsen's catalytic asymmetric epoxidation are the key steps. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.10.040

文献信息

• Reverse asymmetric catalytic epoxidation of unfunctionalized alkenes
  作者：Andreas Scheurer、Paul Mosset、Martina Spiegel、Rolf W. Saalfrank

  DOI：10.1016/s0040-4020(98)01106-5

  日期：1999.1

  from tartaric-derived alicyclic C2 symmetric vicinal diamines were studied in the catalysis of the asymmetric epoxidation of unfunctionalized alkenes. Although the enantioselectivities obtained were not as high as for Jacobsen and Katsuki catalysts, the most striking result was the reversed asymmetric induction.

  研究了由酒石酸脂环族C 2对称邻位二胺制备的新的Salen Mn（III）配合物在未官能化烯烃的不对称环氧化反应中的催化作用。尽管所获得的对映选择性不如Jacobsen和Katsuki催化剂高，但最显着的结果是反向不对称诱导。
• Reusable chiral macrocyclic Mn(III) salen complexes for enantioselective epoxidation of nonfunctionalized alkenes
  作者：Rukhsana I. Kureshy、Tamal Roy、Noor-ul H. Khan、Sayed H.R. Abdi、Arghya Sadhukhan、Hari C. Bajaj

  DOI：10.1016/j.jcat.2011.10.011

  日期：2012.2

  A series of new chiral monomeric and dimeric macrocyclic Mn(III) salen complexes 1–4 with trigol linker were synthesized, characterized (by microanalysis, IR spectroscopy, UV–vis. spectroscopy, optical rotation, and mass spectrometry), and used as catalysts in the enantioselective epoxidation of styrene, cis β-methyl styrene, indene, and chromenes in the presence of several N-oxides as an axial base

  一系列新的手性单体和二聚体大环的Mn（III）萨伦络合物的1 - 4与trigol接头合成，其特征在于（由元素分析，红外光谱，UV-可见光谱，旋光度，和质谱法），和用作催化剂苯乙烯，顺式β-甲基苯乙烯，茚和色烯的对映选择性环氧化反应，在0°C下存在几种N-氧化物作为轴向碱，NaOCl作为氧化剂。通过使用手性二聚大环催化剂3（2.5 mol％），可以以优异的收率（> 99％）和对映选择性（ee在某些情况下高达98％）获得对映纯的环氧化物。复杂4展示了回收利用（在保留对映体选择性的情况下最多可循环研究六个循环）在苯乙烯的不对称环氧化中。配合物4的动力学研究以苯乙烯的环氧化为代表底物，显示出对催化剂和氧化剂的一级依赖性，但与底物的初始浓度无关。
• Synthesis of Metal–(Pentadentate-Salen) Complexes: Asymmetric Epoxidation with Aqueous Hydrogen Peroxide and Asymmetric Cyclopropanation (salenH2:N,N′-bis(salicylidene)ethylene-1,2-diamine)
  作者：Hiroaki Shitama、Tsutomu Katsuki

  DOI：10.1002/chem.200601420

  日期：2007.6.4

  manganese(III) and cobalt(II) complexes, in which the fifth ligand is expected to intramolecularly coordinate to the metal center and exert a trans effect. Indeed, high enantioselectivity has been achieved in epoxidations using aqueous hydrogen peroxide as the terminal oxidant and in cyclopropanations with these complexes as catalysts. In general, metallosalen-catalyzed reactions have been carried out

  众所周知，使用金属氯辛烯（salenH（2）：N，N'-双（水杨基）乙烯-1,2-二胺）配合物作为催化剂的环氧化和环丙烷化的速率和立体化学结果会受到反式作用的影响。复杂的顶端配体。考虑到这种反式效应，我们合成了带有咪唑或吡啶衍生物作为第五配位基团的旋光五齿萨伦配体，并制备了相应的锰（III）和钴（II）配合物，其中第五配体为预期在分子内与金属中心配位并产生反式效应。实际上，在使用过氧化氢水溶液作为末端氧化剂的环氧化反应中以及在使用这些配合物作为催化剂的环丙烷化反应中，已经实现了高对映选择性。一般来说，在过量供体配体的存在下进行了金属氯烯催化的反应。然而，本反应不需要添加任何额外的供体配体。
• Manganese complexes with non-porphyrin N₄ligands as recyclable catalyst for the asymmetric epoxidation of olefins
  作者：Nabin Ch. Maity、Prasanta Kumar Bera、Debashis Ghosh、Sayed H. R. Abdi、Rukhsana I. Kureshy、Noor-ul H. Khan、Hari C. Bajaj、E. Suresh

  DOI：10.1039/c3cy00528c

  日期：——

  complexes of N4 ligands derived from 2-acetylpyridine were prepared and used as catalysts in the enantioselective epoxidation of olefins, using H2O2 as an oxidant to give epoxides, with excellent conversions (up to 99%) and enantiomeric excess (up to 88%) within 1 h at 0 °C. A detailed mechanistic study was undertaken based on the information obtained by single crystal X-ray, optical rotation, UV-Vis

  制备了由2-乙酰基吡啶衍生的N 4配体的新手性锰配合物，并用作烯烃的对映选择性环氧化的催化剂，使用H 2 O 2作为氧化剂生成环氧化物，具有优异的转化率（高达99％）和对映体过量（最高88％）在0°C下1小时内。根据单晶X射线，旋光，UV-Vis，CD光谱和动力学研究获得的信息进行了详细的机理研究，结果表明该反应对于催化剂和氧化剂的浓度是一阶的，并且是独立的。底物浓度。配合物（0.1 mol％）已成功进行了3个循环的苯乙烯与H 2 O环氧化的可循环性实验2在0°C时作为氧化剂和乙酸作为添加剂，并保持了性能。
• Synthesis and Conformational Study of a Novel Macrocyclic Chiral(Salen) ligand and its Uranyl and Mn Complexes
  作者：Maria E. Amato、Francesco P. Ballistreri、Andrea Pappalardo、Gaetano A. Tomaselli、Rosa M. Toscano

  DOI：10.3390/molecules15031442

  日期：——

  A novel chiral macrocyclic ligand incorporating a chiral salen moiety into a framework containing two biphenyl units was synthesized. Structural properties and conformational aspects of the free ligand and an UO2 complex were studied by using NMR spectroscopy in solution and MM calculations. The Mn(III) complex was tested as catalyst in enantioselective oxidation of prochiral unfunctionalized olefins

  合成了一种新型手性大环配体，该配体将手性 salen 部分结合到包含两个联苯单元的框架中。通过使用溶液中的 NMR 光谱和 MM 计算来研究游离配体和 UO2 复合物的结构特性和构象方面。在非常温和的条件下，将 Mn(III) 配合物用作将前手性未官能化烯烃对映选择性氧化成相应光学活性环氧化物的催化剂。