5-bromo-3-coumarincarboxylic acid | 54682-43-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: 5-bromo-3-coumarincarboxylic acid
• 英文别名: 5-bromo-2-oxo-2H-chromene-3-carboxylic acid；5-bromo-2-oxochromene-3-carboxylic acid
• CAS: 54682-43-8
• 化学式: C₁₀H₅BrO₄
• 分子量: 269.051
• InChiKey: YQWJEBREUGTJPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-bromo-3-coumarincarboxylic acid 在 溶剂黄146 、 silver carbonate 作用下， 以 2,4-滴二甲胺盐 为溶剂， 反应 16.0h， 以58%的产率得到5-溴-2H-色烯-2-酮
  参考文献：
  名称：

  银催化香豆素-3-羧酸的轻松脱羧

  摘要：

  已经开发了具有温和反应条件的简单且高效的方案，该方案允许各种功能化的香豆素-3-羧酸的平滑的丙级羧化。在催化量的Ag 2 CO 3和乙酸的存在下，即使未活化的香豆素-3-羧酸也以良好的产率转化为优异的产率，并且易于制备成相应的香豆素衍生物。

  DOI：

  10.1016/j.tet.2010.10.019
• 作为产物：
  描述：

  ethyl 5-bromo-2-oxo-2H-chromene-3-carboxylate 在 sodium hydroxide 作用下， 反应 2.0h， 以47%的产率得到5-bromo-3-coumarincarboxylic acid
  参考文献：
  名称：

  Coumarin as Attractive Casein Kinase 2 (CK2) Inhibitor Scaffold: An Integrate Approach To Elucidate the Putative Binding Motif and Explain Structure–Activity Relationships

  摘要：

  Casein kinase 2 (CK2) is an ubiquitous, essential, and highly pleiotropic protein kinase whose abnormally high constitutive activity is suspected to underlie its pathogenic potential in neoplasia and other diseases. Recently, using different virtual screening approaches, we have identified several novel CK2 inhibitors. In particular, we have discovered that coumarin moiety can be considered an attractive CK2 inhibitor scaffold. In the present work, we have synthetized and tested a small library of coumarins (more than 60), rationalizing the observed structure-activity relationship. Moreover, the most promising inhibitor, 3,8-dibromo-7-hydroxy-4-methylchromen-2-one (DBC), has been also crystallized in complex with CK2, and the experimental binding mode has been used to derive a linear interaction energy (LIE) model.

  DOI：

  10.1021/jm070909t

文献信息

• Design and Synthesis of Chiral<i>oxa</i>-Spirocyclic Ligands for Ir-Catalyzed Direct Asymmetric Reduction of Bringmann’s Lactones with Molecular H₂
  作者：Gen-Qiang Chen、Bi-Jin Lin、Jia-Ming Huang、Ling-Yu Zhao、Qi-Shu Chen、Shi-Peng Jia、Qin Yin、Xumu Zhang

  DOI：10.1021/jacs.8b03642

  日期：2018.7.5

  synthesis include the construction of the all-carbon quaternary center at an early stage, a key double intramolecular SNAr step to introduce the spirocycles and the feasibility of operating on >100 g scale. Both enantiomers of O-SPINOL can be easily accessed through optical resolution with l-proline by control of the solvent. The chiral tridentate ligand O-SpiroPAP derived from O-SPINOL has been successfully

  我们在此提出了一种简便且无柱的合成路线，用于合成结构独特的氧杂-螺环二酚，称为 O-SPINOL。该合成的特点包括在早期构建全碳四元中心、引入螺环的关键双分子内 SNAr 步骤以及在 >100 g 规模上操作的可行性。O-SPINOL 的两种对映异构体都可以通过控制溶剂的 l-脯氨酸光学拆分轻松获得。衍生自 O-SPINOL 的手性三齿配体 O-SpiroPAP 已成功合成并应用于在温和反应条件下铱催化的桥联联芳基内酯的不对称氢化，以优异的产率和对映选择性（高达 99 % 产率和 >99% ee）。
• CuH-Catalyzed Atropoenantioselective Reduction of Bringmann’s Lactones via Dynamic Kinetic Resolution
  作者：Le’an Hu、Yao Zhang、Gen-Qiang Chen、Bi-Jin Lin、Qing-Wen Zhang、Qin Yin、Xumu Zhang

  DOI：10.1021/acs.orglett.9b01907

  日期：2019.7.19

  a broad substrate scope and good functional group tolerance and allows the rapid assembly of various valuable axially chiral biaryls in good to high yields (up to 92% yield) with high to excellent enantioselectivities (up to 96% ee). Moreover, this report represents a rare example that a carbonyl group of esters is reduced under homogeneous asymmetric CuH catalysis.

  已经公开了经由动态动力学拆分的CuH催化的Bringmann内酯的促熵还原选择性还原。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高到高的收率（高达92％的收率）以及高到出色的对映选择性（高达96％ee）快速组装各种有价值的轴向手性联芳基。此外，该报告代表了一个罕见的例子，即酯的羰基在均相不对称CuH催化下被还原。
• Silver-catalyzed facile decarboxylation of coumarin-3-carboxylic acids
  作者：Farnaz Jafarpour、Nafiseh Jalalimanesh、Mina Barzegar Amiri Olia、Asieh Otaredi Kashani

  DOI：10.1016/j.tet.2010.10.019

  日期：2010.12

  protocol with mild reaction conditions has been developed that allows the smooth protiodecarboxylation of diversely functionalized coumarin-3-carboxylic acids. In the presence of catalytic amounts of Ag2CO3 and acetic acid, even un-activated coumarin-3-carboxylic acids were converted in good to excellent yields and with great preparative ease to the corresponding coumarin derivatives.

  已经开发了具有温和反应条件的简单且高效的方案，该方案允许各种功能化的香豆素-3-羧酸的平滑的丙级羧化。在催化量的Ag 2 CO 3和乙酸的存在下，即使未活化的香豆素-3-羧酸也以良好的产率转化为优异的产率，并且易于制备成相应的香豆素衍生物。
• Coumarin as Attractive Casein Kinase 2 (CK2) Inhibitor Scaffold: An Integrate Approach To Elucidate the Putative Binding Motif and Explain Structure–Activity Relationships
  作者：Adriana Chilin、Roberto Battistutta、Andrea Bortolato、Giorgio Cozza、Samuele Zanatta、Giorgia Poletto、Marco Mazzorana、Giuseppe Zagotto、Eugenio Uriarte、Adriano Guiotto、Lorenzo A. Pinna、Flavio Meggio、Stefano Moro

  DOI：10.1021/jm070909t

  日期：2008.2.1

  Casein kinase 2 (CK2) is an ubiquitous, essential, and highly pleiotropic protein kinase whose abnormally high constitutive activity is suspected to underlie its pathogenic potential in neoplasia and other diseases. Recently, using different virtual screening approaches, we have identified several novel CK2 inhibitors. In particular, we have discovered that coumarin moiety can be considered an attractive CK2 inhibitor scaffold. In the present work, we have synthetized and tested a small library of coumarins (more than 60), rationalizing the observed structure-activity relationship. Moreover, the most promising inhibitor, 3,8-dibromo-7-hydroxy-4-methylchromen-2-one (DBC), has been also crystallized in complex with CK2, and the experimental binding mode has been used to derive a linear interaction energy (LIE) model.