(3R,4R)-3,4-epoxy-2,2-dimethyl-6-nitrochromane

• 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-2,2-dimethyl-6-nitrochromane
• 英文别名: (1aR,7bR)-2,2-dimethyl-6-nitro-1a,7b-dihydrooxireno[2,3-c]chromene
• 化学式: C₁₁H₁₁NO₄
• 分子量: 221.213
• InChiKey: VSLNFOJWTXTUMK-NXEZZACHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  67.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,4R)-3,4-epoxy-2,2-dimethyl-6-nitrochromane 在 氨 作用下， 以 乙醇 为溶剂， 生成 trans-4-Amino-3,4-dihydro-3-hydroxy-2,2-dimethyl-6-nitro-2H-1-benzopyran
  参考文献：
  名称：

  新型反式-4-（取代的苯甲酰胺基）-3,4-二氢-2H-苯并[b]-吡喃-3-醇衍生物的合成作为潜在的具有独特结合特征的抗惊厥药。

  摘要：

  DOI：

  10.1021/jm960535w
• 作为产物：
  描述：

  4-硝基苯基乙酸酯 在 四氢吡咯 、 aluminum (III) chloride 、 sodium hypochlorite 、 sodium tetrahydroborate 、 disodium hydrogenphosphate 、 (-)-chloro((1R,2R)-4,4',6,6'-tetra-tert-butyl-2,2'-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato)manganese(III) 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 4.0h， 生成 (3R,4R)-3,4-epoxy-2,2-dimethyl-6-nitrochromane
  参考文献：
  名称：

  Identification of 3-hydroxy-4[3,4-dihydro-3-oxo-2H-1,4-benzoxazin-4-yl]-2,2-dimethyldihydro-2H-benzopyran derivatives as potassium channel activators and anti-inflammatory agents

  摘要：

  The present study described the design, synthesis and identification of 3-hydroxy-4[3,4-dihydro-3-oxo-2H-1,4-benzoxazin-4-yl]-2,2-dimethyldihydro-2H-benzopyran derivatives. Their biological activity was tested for K-ATP channel opener as antihypertensives, COX-1 and COX-2 activity. The results were compared with the activity of cromakalim, ibuprofen and celecoxib. The study aimed at exploring the influence of introduction of a benzoxazine substituent at position 6 of various derivatives of benzopyrans in order to improve biological activity. Several compounds were found to be equipotent or even more potent than cromakalim. Out of these nitro-substituted benzopyrans, nitro substitution at benzoxazino group possessed potent antihypertensive activity in the R/S isomers. With amino derivatives, activity remains constant when compared with standard cromakalim. Similarly, compounds 17b, 17c, 17e and 17h have exhibited around 40 % inhibition of COX-1 as compared to the inhibition of COX-2. Only two compounds 17g and 17i exhibited effective inhibition more than 50 % of COX-2 compared with the inhibition of COX-1 at a concentration of 0.3 mg/ml.

  DOI：

  10.1007/s00044-015-1344-6

文献信息

• 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。
• Synthesis and Antihypertensive Activity of 4-(Diazabicyclo[4.1.0]-heptenyloxy)benzopyran Derivatives and Their Analogues.
  作者：Haruhiko HORINO、Tetsuya MIMURA、Katsuji KAGECHIKA、Masahiro OHTA、Hideo KUBO、Masayuki KITAGAWA

  DOI：10.1248/cpb.46.602

  日期：——

  0]hept- 2-en-2-yl)oxy]-2H-1-benzopyrans and their analogues were synthesized and evaluated on potassium channel opening and hypotensive activities. Compound (-)-13B with a (4-methyl-5-oxo-3,4-diazabicyclo[4.1.0]hept-2-en-2-yl)oxy group for the 4-position of the benzopyran ring was 3 times as potent as EMD 57283 (II), the lead compound, in hypotensive activity. The results would demonstrate that 5-oxo-3,4-diazabicyclo[4

  一系列的3,4-二氢-3-羟基-4-[（5-氧代-3,4-二氮杂双环[4.1.0]庚二-2-烯-2-基）氧基] -2H-1-苯并吡喃和合成了它们的类似物，并对钾通道的开放和降压活性进行了评估。对于苯并吡喃环的4-位具有（4-甲基-5-氧代-3,4-二氮杂双环[4.1.0]庚-2-烯-2-基）氧基的化合物（-）-13B为3在降压活动中的功效是主要化合物EMD 57283（II）的两倍。结果表明5-氧代-3，4-二氮杂双环[4.1.0]庚-2-烯-2-基氧基部分作为苯并吡喃型钾通道开放剂的4-位上的取代基是有效的。
• Asymmetric Epoxidation Using Iminium Salt Organocatalysts Featuring Dynamically Controlled Atropoisomerism
  作者：Philip C. Bulman Page、Christopher J. Bartlett、Yohan Chan、David Day、Phillip Parker、Benjamin R. Buckley、Geracimos A. Rassias、Alexandra M. Z. Slawin、Steven M. Allin、Jérôme Lacour、André Pinto

  DOI：10.1021/jo300915u

  日期：2012.7.20

  Introduction of a pseudoaxial substituent at a stereogenic center adjacent to the nitrogen atom in binaphthyl- and biphenyl-derived azepinium salt organocatalysts affords improved enantioselectivities and yields in the epoxidation of unfunctionalized alkenes. In the biphenyl-derived catalysts, the atropoisomerism at the biphenyl axis is controlled by the interaction of this substituent with the chiral

  在衍生自双萘基和联苯的氮杂吡啶鎓盐有机催化剂中与氮原子相邻的立体中心处引入假轴取代基，可提高对映选择性，并提高未官能化烯烃的环氧化收率。在联苯衍生的催化剂中，联苯轴上的对映异构通过该取代基与氮上的手性取代基的相互作用来控制。
• Design and Assembly of a Chiral Metallosalen-Based Octahedral Coordination Cage for Supramolecular Asymmetric Catalysis
  作者：Chunxia Tan、Jingjing Jiao、Zijian Li、Yan Liu、Xing Han、Yong Cui

  DOI：10.1002/anie.201711310

  日期：2018.2.19

  and high enantioselectivity represent a design challenge of practical importance. Herein, it is demonstrated that a chiral octahedral coordination cage can be constructed by using twelve enantiopure Mn(salen)‐derived dicarboxylic acids as linear linkers and six Zn4‐p‐tert‐butylsulfonylcalix[4]arene clusters as tetravalent four‐connected vertices. The porous cage features a large hydrophobic cavity (≈3944 Å3)

  具有高催化活性和高对映选择性的超分子容器代表了具有实际重要性的设计挑战。本文中，证实通过使用手性八面体配位笼可以被构造12对映体纯的Mn（沙仑）衍生的二羧酸作为线性接头和6的Zn 4 -对-叔-butylsulfonylcalix [4]芳烃簇四价四连接的顶点。多孔笼设有一个大的疏水性空腔（≈3944埃3）装饰有催化活性的金属硅铝烯物种，并被证明是一种高效且可回收的不对称催化剂，可用于消旋外消旋仲醇的氧化动力学拆分和烯烃的环氧化，对映体过量可达> 99％。笼式结构不仅可以防止分子间失活，并能稳定Mn（salen）催化剂，而且可以将底物包封并在空腔中浓缩反应物，从而相对于游离的金属硅铝催化剂而言，具有更高的反应性和对映选择性。
• 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。