3-nitro-2-phenyl-2H-chromene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: 3-nitro-2-phenyl-2H-chromene
• 英文别名: (2R)-3-nitro-2-phenyl-2H-chromene
• 化学式: C₁₅H₁₁NO₃
• 分子量: 253.257
• InChiKey: ULXCGRAUCRLSRG-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  β-硝基苯乙烯 、 salicyl N-tosylimine 在 N-[3,5-双(三氟甲基)苯基]-N'-[(8a,9S)-6'-甲氧基-9-金鸡宁]硫脲 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以31%的产率得到3-nitro-2-phenyl-2H-chromene
  参考文献：
  名称：

  双功能硫脲催化对映选择性合成2-Aryl-3-nitro-2H-chromenes

  摘要：

  双功能硫脲催化的oxa-Michael-aza-Henry-脱磺酰胺串联方法用于合成手性2-芳基-3-硝基-2H-色烯。该方法以中等至良好的产率和对映选择性直接获得相应的产品。

  DOI：

  10.1055/s-0030-1259956

文献信息

• Heterogeneous enantioselective synthesis of chromans via the oxa-Michael–Michael cascade reaction synergically catalyzed by grafted chiral bases and inherent hydroxyls on mesoporous silica surface
  作者：Shanshan Wang、Jing He、Zhe An

  DOI：10.1039/c7cc03556j

  日期：——

  A heterogeneous enantioselective oxa-Michael–Michael reaction for the synthesis of chromans has been developed on a heterogeneous acid–base synergic catalyst with inherent silica as acidic sites and immobilized chiral amines as basic sites. Final products were afforded in selectivity of up to 98% and ee of 97% from 2-nitrovinyl phenol and 3-methyl-2-butenal. The heterogeneous synergistic catalytic

  已经开发了一种多相对映选择性的氧杂-Michael-Michael反应，用于合成苯并二氢吡喃，该反应以固有的二氧化硅为酸性位点和固定的手性胺为碱性位点的多相酸碱协同催化剂为基础。与2-硝基乙烯基苯酚和3-甲基-2-丁烯醛相比，最终产品具有高达98％的选择性和ee达97％的选择性。还研究了多相协同催化机理。
• Asymmetric Direct Michael Reactions of Cyclohexanone with Aromatic Nitroolefins in Water Catalyzed by Novel Axially Unfixed Biaryl-Based Bifunctional Organocatalysts
  作者：Hong-Wu Zhao、Zhao Yang、Yuan-Yuan Yue、Hai-Long Li、Xiu-Qing Song、Zhi-Hui Sheng、Wei Meng、Xiao-Yu Guo

  DOI：10.1055/s-0033-1340289

  日期：——

  new family of axially unfixed biaryl-based water-compatible bifuctional organocatalysts were designed and synthesized for the asymmetric direct Michael reaction of cyclohexanone with various nitroolefins in water. One of the organocatalysts incorporates pyrrolidine and arylsulfonamide motifs as active organocatalytic sites, and axially unfixed biaryl as a skeleton; with this organocatalyst, the direct

  设计并合成了一类新的轴向未固定联芳基水相容双功能有机催化剂，用于环己酮与水中各种硝基烯烃的不对称直接迈克尔反应。其中一种有机催化剂包含吡咯烷和芳基磺酰胺基序作为活性有机催化位点，以及轴向未固定的联芳基作为骨架；使用这种有机催化剂，直接迈克尔反应很容易进行，以高产率（高达 99% 的产率）提供所需的迈克尔加合物，并具有高水平的立体控制（高达 >99:1 dr 和 94% ee）。
• Augmentation of Enantioselectivity by Spatial Tuning of Aminocatalyst: Synthesis of 2-Alkyl/aryl-3-nitro-2<i>H</i>-chromenes by Tandem Oxa-Michael–Henry Reaction
  作者：Rahul Mohanta、Ghanashyam Bez

  DOI：10.1021/acs.joc.9b03366

  日期：2020.4.3

  The asymmetric oxa-Michael addition of salicylaldehyde to conjugated nitroalkenes often suffers from poor reactivity and selectivity and a long reaction time. Because of the formation of an iminium ion with aminocatalyst, the nucleophilicity of the phenolic hydroxy group in salicylaldehyde reduces further to make the oxa-Michael reaction reversible. Here, we report a structurally simple and easily

  水杨醛向共轭硝基烯烃的不对称氧杂-迈克尔加成反应通常具有较差的反应性和选择性以及较长的反应时间。由于与氨基催化剂形成亚胺离子，因此水杨醛中酚羟基的亲核性进一步降低，从而使氧杂-迈克尔反应可逆。这里，我们报告一个结构简单且容易接近升-脯氨酸衍生aminocatalyst，苯基升-脯氨酰胺，为水杨醛的不对称串联氧杂迈克尔-亨利反应与共轭硝基烯，得到2-烷基/芳基-3-硝基-2- ħ -色烯在较短的反应时间内具有出色的对映选择性。
• Synthesis of substituted chiral chromans via organocatalytic kinetic resolution of racemic 3-nitro-2-aryl-2H-chromenes with ketones catalyzed by pyrrolidinyl-camphor-derived organocatalysts
  作者：Dhananjay R. Magar、Kwunmin Chen

  DOI：10.1016/j.tet.2012.05.019

  日期：2012.7

  pyrrolidinyl-camphor derivative 2b as a bifunctional organocatalyst under neat conditions in the presence of AcOH at 0 °C. In general, the organocatalytic asymmetric Michael addition of ketones proceeded smoothly to give the functionalized Michael adducts (3a–n) with good-to-high diastereo- and enantioselectivities (up to 92:8 dr, 93% ee, and 47% yield). The less reactive chromenes (S)-1a–h, k, l and (R)-1i–j were

  在0°C存在AcOH的纯净条件下，使用吡咯烷基-樟脑樟衍生物2b作为双功能有机催化剂，探索了外消旋的2-芳基-3-硝基-2 H-苯甲基（1a – l）的动力学拆分。通常，酮的有机催化不对称迈克尔加成反应顺利进行，从而使官能化迈克尔加合物（3a - n）具有良好至高的非对映体和对映体选择性（高达92：8 dr，93％ee和47％的收率） 。活性较低的色烯（S）-1a – h，k，l和（R）-1i–以高化学产率和中等光学纯度（高达42％的化学产率和72％的ee）回收了j。
• A Novel Enantioselective Catalytic Tandem Oxa-Michael-Henry Reaction: One-Pot Organocatalytic Asymmetric Synthesis of 3-Nitro-2<i>H</i>-chromenes
  作者：Dan-Qian Xu、Yi-Feng Wang、Shu-Ping Luo、Shuai Zhang、Ai-Guo Zhong、Hui Chen、Zhen-Yuan Xu

  DOI：10.1002/adsc.200800535

  日期：2008.11.3

  An enantioselective oxa-Michael–Henry reaction of substituted salicylaldehydes with nitroolefins that proceeds though an aromatic iminium activation (AIA) has been developed by using a chiral secondary amine organocatalyst and salicylic acid as a co-catalyst. The corresponding 3-nitro-2H-chromenes were obtained in moderate-to-good yields with up to 91% ee under mild conditions. Based on the experimental

  通过使用手性仲胺有机催化剂和水杨酸作为助催化剂，开发了取代的水杨醛与硝基烯烃的对映选择性氧杂-迈克尔-亨利反应，该反应通过芳香亚胺活化（AIA）进行。在温和条件下，以中等至良好的收率获得了相应的3-硝基-2 H-色烯，其中ee高达91％。基于实验结果和中间体的ESI质谱检测，已提出了一个合理的过渡态来解释激活和不对称诱导的起源。