ethyl (R)-2-(6-bromo-4-oxochroman-3-yl)acetate | 1016976-50-3

• 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: ethyl (R)-2-(6-bromo-4-oxochroman-3-yl)acetate
• 英文别名: ethyl 2-[(3R)-6-bromo-4-oxo-2,3-dihydrochromen-3-yl]acetate
• CAS: 1016976-50-3
• 化学式: C₁₃H₁₃BrO₄
• 分子量: 313.148
• InChiKey: DYNAEEFUPQKZEE-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  Ethyl 4-(4-bromo-2-formylphenoxy)-2-butenoate 在 （5aS，6R，9S，9aR）-5a，6,7,8,9,9a-六氢-6,11,11-三甲基-2-（2,3,4,5,6-五氟苯基）-6，9-甲基-4H-[1,2,4]三唑[3,4-c][1,4]苯并恶嗪四氟硼酸酯 、 N,N-二异丙基乙胺 作用下， 以 邻二甲苯 为溶剂， 反应 4.0h， 以94%的产率得到ethyl (R)-2-(6-bromo-4-oxochroman-3-yl)acetate
  参考文献：
  名称：

  d-Camphor-Derived Triazolium Salts for Enantioselective Intramolecular Stetter Reactions

  摘要：

  基于樟脑骨架的手性三唑盐被证明对不对称分子内斯特特反应非常有效。在催化剂的用量达到10 mol%时，所需产物可获得高达97%的ee，收率极佳。

  DOI：

  10.1055/s-0030-1259732

文献信息

• Solvent-Free Benzoin and Stetter Reactions with a Small Amount of NHC Catalyst in the Liquid or Semisolid State
  作者：Tadashi Ema、Yoshiko Nanjo、Sho Shiratori、Yuta Terao、Ryo Kimura

  DOI：10.1021/acs.orglett.6b03115

  日期：2016.11.4

  The intermolecular or intramolecular asymmetric benzoin reaction was catalyzed by a small amount of N-heterocyclic carbene (NHC) (0.2–1 mol %) under solvent-free conditions. The solvent-free intramolecular asymmetric Stetter reaction also proceeded efficiently with NHC (0.2–1 mol %). In some cases, even solid-to-solid or solid-to-liquid conversions took place with low catalyst loading (0.2–1 mol %)

  在无溶剂条件下，少量的N-杂环卡宾（NHC）（0.2-1 mol％）催化分子间或分子内不对称安息香反应。使用NHC（0.2–1 mol％），无溶剂的分子内不对称Stetter反应也能有效地进行。在某些情况下，即使在催化剂负载量较低（0.2–1摩尔％）的情况下，也可以进行固-固或固-液转化。
• Synthesis of (1R,2R)-DPEN-derived triazolium salts and their application in asymmetric intramolecular Stetter reactions
  作者：Min-Qiang Jia、Yi Li、Zi-Qiang Rong、Shu-Li You

  DOI：10.1039/c1ob00025j

  日期：——

  A series of novel chiral triazolium salts has been synthesized from readily available (1R,2R)-DPEN and found to be efficient for the enantioselective intramolecular Stetter reaction. With 10 mol% of the catalyst, the intramolecular Stetter reaction was realized in excellent yields with up to 97% ee.

  研究人员利用容易获得的 (1R,2R)-DPEN 合成了一系列新型手性三唑鎓盐，并发现它们能有效地进行对映选择性分子内斯泰特反应。在催化剂用量为 10 mol% 的情况下，分子内 Stetter 反应的产率极高，ee 值高达 97%。
• Scope of the Asymmetric Intramolecular Stetter Reaction Catalyzed by Chiral Nucleophilic Triazolinylidene Carbenes
  作者：Javier Read de Alaniz、Mark S. Kerr、Jennifer L. Moore、Tomislav Rovis

  DOI：10.1021/jo702313f

  日期：2008.3.1

  A highly enantioselective intramolecular Stetter reaction of aromatic and aliphatic aldehydes tethered to different Michael acceptors has been developed. Two triazolium scaffolds have been identified that catalyze the intramolecular Stetter reaction with good reactivity and enantioselectivity. The substrate scope has been examined and found to be broad; both electron-rich and -poor aromatic aldehydes

  芳香族和脂肪族醛与不同迈克尔受体的高度对映选择性分子内 Stetter 反应已被开发出来。已鉴定出两种三唑鎓支架以良好的反应性和对映选择性催化分子内 Stetter 反应。底物范围已经过检查，发现范围很广；富电子和贫电子芳香醛均以高产率和对映选择性进行环化。系链可以包括氧、硫、氮和碳连接体而没有不利影响。此外，各种束缚迈克尔受体的结合包括酰胺、酯、硫酯、酮、醛和腈。催化剂负载量可以降低到 3 mol%，而不会显着影响反应的反应性或选择性。
• Immobilization of Privileged Triazolium Carbene Catalyst for Batch and Flow Stereoselective Umpolung Processes
  作者：Daniele Ragno、Graziano Di Carmine、Arianna Brandolese、Olga Bortolini、Pier Paolo Giovannini、Alessandro Massi

  DOI：10.1021/acscatal.7b02164

  日期：2017.9.1

  A strategy for the immobilization of the valuable triazolium carbene Rovis catalyst onto polystyrene and silica supports is presented. Initially, the catalyst activity and recyclability were tested under batch conditions in the model stereoselective intramolecular Stetter reaction leading to optically active chromanones. Good results in terms of yield (95%) and enantioselectivity (ee 81–95%) were detected

  提出了一种将有价值的三唑碳烯罗维斯催化剂固定在聚苯乙烯和二氧化硅载体上的策略。最初，在分批条件下在模型立体选择性分子内斯特斯特反应中测试了催化剂的活性和可循环性，该反应导致了旋光的苯并二氢吡喃酮。对于聚苯乙烯负载的催化剂（10摩尔％），在产率（95％）和对映选择性（ee 81–95％）方面，均获得了良好的结果，而对于二氧化硅负载的类似物，却获得了较差的结果。还，
• An asymmetric intramolecular Stetter reaction catalyzed by a chiral triazolium precatalyst bearing a pyridine moiety
  作者：Takahiro Soeta、Yuhta Tabatake、Yutaka Ukaji

  DOI：10.1016/j.tet.2012.09.095

  日期：2012.12

  A number of chiral triazolium salts incorporating pyridine rings have been investigated as precatalysts for an asymmetric intramolecular Stetter reaction. The salt structure and reaction parameters were optimized, resulting in very good yield and enantioselectivity. This reaction was found to be applicable to a wide range of salicylaldehyde-derived substrates. (C) 2012 Elsevier Ltd. All rights reserved.