(S)-2-(4-methoxyphenyl)-3-nitro-2H-chromene | 1384100-25-7

• 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: (S)-2-(4-methoxyphenyl)-3-nitro-2H-chromene
• 英文别名: 3-nitro-2-(4-methoxyphenyl)-2H-chromene；(2S)-2-(4-methoxyphenyl)-3-nitro-2H-chromene
• CAS: 1384100-25-7
• 化学式: C₁₆H₁₃NO₄
• 分子量: 283.284
• InChiKey: VWHLPNCPVHZLQX-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2-(4-methoxyphenyl)-3-nitro-2H-chromene 、 N-methylnitrone 以52%的产率得到
  参考文献：
  名称：

  HARAN, S. HARI;MATHUR, H. H.;TRIVEDI, G. K., INDIAN J. CHEM. B, 27,(1988) N1, C. 994-996

  摘要：

  DOI：
• 作为产物：
  描述：

  1-(4-甲氧苯基)-2-硝基乙烯 、 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， 生成 2-(4-methoxyphenyl)-3-nitro-2H-chromene 、 (S)-2-(4-methoxyphenyl)-3-nitro-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

• 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。
• Efficient kinetic resolution of racemic 3-nitro-2H-chromene derivatives catalyzed by Takemoto's organocatalyst
  作者：Jian-Wu Xie、Li-Ping Fan、Hong Su、Xin-Sheng Li、Dong-Cheng Xu

  DOI：10.1039/b922668k

  日期：——

  Efficient kinetic resolution of racemic 3-nitro-2H-chromenes by bifunctional thiourea afforded optically active (R)-3-nitro-2H-chromene derivatives with moderate to good enantioselectivities, which simultaneously gave the multifunctional 3,4-diphenyl-3a-nitrobenzopyrano-[3,4-c]-pyrrolidine-1,1-dicarboxylate derivatives with four vicinal chiral carbon centers.

  通过双官能硫脲对外消旋 3-硝基-2H-苯进行高效动力学解析，得到了具有光学活性的(R)-3-硝基-2H-苯衍生物，其对映体选择性为中等至良好，同时还得到了具有四个手性碳中心的多功能 3,4-二苯基-3a-硝基苯并吡喃-[3,4-c]-吡咯烷-1,1-二甲酸酯衍生物。
• Aqueous synthesis of 2-aryl-3-nitro-2H chromenes via l-prolinamide mediated tandem oxa-Michael Henry reactions
  作者：Dixita Rani、Vinny Gulati、Mamta Guleria、Satya Prakash Singh、Jyoti Agarwal

  DOI：10.1016/j.molstruc.2022.133341

  日期：2022.10

  An efficient and aqueous protocol has been developed for the synthesis of 2-aryl-3-nitro-2H-chromene derivatives. This protocol involves the l-prolinamide mediated tandem oxa-Michael Henry reaction between a variety of β-nitrostyrenes and salicylaldehyde. Among the screened solvents, the catalytic efficiency of prolinamides was found to be high in chloroform, but the best results were obtained in water

  已经开发了一种用于合成 2-芳基-3-硝基-2H-色烯衍生物的有效和水性方案。该协议涉及l-脯氨酰胺介导的串联氧杂-迈克尔亨利反应在各种 β-硝基苯乙烯和水杨醛之间。在筛选的溶剂中，发现脯氨酰胺在氯仿中的催化效率很高，但在水中获得了最好的结果，从而以优异的收率提供了 2-苯基-3-硝基-2H-色烯。还使用各种取代的 β-硝基苯乙烯研究了底物范围。所有反应都很好地以非常高的产率提供相应的产物。进行理论计算以找出反应途径和过渡态的性质在 3-21G* 基组和对应于产物的 TS1 ( S)-3a 比对应于产物 ( R )-3a 的 TS2 高 1.13 kcal/mol。
• The Role of L-Proline and Co-Catalysts in the Enantioselectivity of OXA-Michael-Henry Reactions
  作者：Lucas do Carmo、Simone Silva、Matheus Machado、Paloma Prata、Alberto Wisniewski Júnior、Diogo Vidal、José Augusto Villar

  DOI：10.21577/0103-5053.20180226

  日期：——

  The use of L-proline derivatives employed in OXA-Michael-Henry tandem reactions has been an efficient method to produce enantiomerically enriched compounds. In this work it was carried out a study of the OXA-Michael-Henry reactions between salicylaldehyde and beta-nitrostyrenes, catalyzed by L-proline and its derivatives. The corresponding (R)-3-nitro-2-phenyl-2H-chromenes were obtained in 55% enantiomeric excess (ee, 20 mol% L-proline) and 70% ee (stoichiometric amount) employing Ti((OPr)-Pr-i)(4) as Lewis acid. Despite the ee obtained, to the best of our knowledge, this result represents the highest enantioselectivity obtained in this reaction. Therefore, this work demonstrated that it is possible to obtain considerable enantiomeric excesses in OXA-Michael-Henry reactions using L-proline, an inexpensive and accessible amino acid.