methyl 6-oxo-6-(quinolin-8-ylamino)hexanoate | 1319744-27-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: methyl 6-oxo-6-(quinolin-8-ylamino)hexanoate
• 英文别名: Methyl 6-oxo-6-(quinolin-8-ylamino)hexanoate
• CAS: 1319744-27-8
• 化学式: C₁₆H₁₈N₂O₃
• 分子量: 286.331
• InChiKey: MJKNMUDLZSCNAA-UHFFFAOYSA-N

物化性质

• 熔点：
  71-72 °C
• 沸点：
  502.3±30.0 °C(Predicted)
• 密度：
  1.213±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  68.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-碘吡啶 、 methyl 6-oxo-6-(quinolin-8-ylamino)hexanoate 在 palladium diacetate 、 磷酸二丁酯 、 silver carbonate 、 sodium iodide 作用下， 以 N,N-二甲基乙酰胺 、 甲苯 为溶剂， 反应 24.0h， 以76%的产率得到
  参考文献：
  名称：

  Synthesis of Alkyl-Substituted Pyridines by Directed Pd(II)-Catalyzed C–H Activation of Alkanoic Amides

  摘要：

  A general alkylation protocol for substituted iodopyridines was developed (32 examples, 44-97% yield). The reaction is based on the Pd(II)-catalyzed C-H activation of 8-aminoquinoline-derived alkanoic amides and it employs a catalyst cocktail of Pd(OAc)(2) (10 mol%), NaI (30 mol%), and (BuO)(2)POOH (20 mol%), with Ag2CO3 as base.

  DOI：

  10.1055/s-0035-1560810
• 作为产物：
  描述：

  8-氨基喹啉 、 甲基脂肪酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 methyl 6-oxo-6-(quinolin-8-ylamino)hexanoate
  参考文献：
  名称：

  Synthesis of Alkyl-Substituted Pyridines by Directed Pd(II)-Catalyzed C–H Activation of Alkanoic Amides

  摘要：

  A general alkylation protocol for substituted iodopyridines was developed (32 examples, 44-97% yield). The reaction is based on the Pd(II)-catalyzed C-H activation of 8-aminoquinoline-derived alkanoic amides and it employs a catalyst cocktail of Pd(OAc)(2) (10 mol%), NaI (30 mol%), and (BuO)(2)POOH (20 mol%), with Ag2CO3 as base.

  DOI：

  10.1055/s-0035-1560810

文献信息

• Palladium-Catalyzed Base-Promoted Arylation of Unactivated C(sp³)-H Bonds by Aryl Iodides: A Practical Approach To Synthesize β-Aryl Carboxylic Acid Derivatives
  作者：Quan Gou、Gang Liu、Lanxiu Zhou、Suiyun Chen、Jun Qin

  DOI：10.1002/ejoc.201701215

  日期：2017.11.16

  A highly efficient protocol for the β-arylation of carboxylic amides by aryl iodides under PdCl2(CH3CN)2/CsOAc catalysis was developed. This method was found to tolerate a broad scope of substrates and was successfully employed in the preparation of a variety of β-aryl α-amino and γ-amino acid derivatives. The utility of this method was further illustrated in the synthesis of the psychotropic drug

  开发了一种高效的方案，用于在 PdCl2(CH3CN)2/CsOAc 催化下芳基碘化物对羧酰胺进行 β-芳基化。发现该方法可耐受广泛的底物，并成功用于制备各种 β-芳基 α-氨基和 γ-氨基酸衍生物。这种方法的效用在精神药物 (±)-phenibut 和 β-芳基胆汁酸类似物的合成中得到了进一步说明。
• Palladium-Catalyzed Direct Ethynylation of C(sp³)–H Bonds in Aliphatic Carboxylic Acid Derivatives
  作者：Yusuke Ano、Mamoru Tobisu、Naoto Chatani

  DOI：10.1021/ja206002m

  日期：2011.8.24

  The first catalytic alkynylation of unactivated C(sp(3))-H bonds has been accomplished. The method allows for the straightforward introduction of an ethynyl group into aliphatic acid derivatives under palladium catalysis. This new reaction can be applied to the rapid elaboration of complex aliphatic acids, for example, via azide/alkyne cycloaddition.

  未活化的 C(sp(3))-H 键的第一次催化炔化已经完成。该方法允许在钯催化下将乙炔基直接引入到脂肪酸衍生物中。这种新反应可用于复杂脂肪酸的快速制备，例如，通过叠氮化物/炔烃环加成反应。
• Transition Metal‐Controlled Direct Regioselective Intermolecular Amidation of C−H Bonds with Azodicarboxylates: Scope, Mechanistic Studies, and Applications
  作者：He‐Yuan Bai、Xin Fu、Jin‐Long Pan、Hai‐Qian Ma、Zhi‐Min Chen、Tong‐Mei Ding、Shu‐Yu Zhang

  DOI：10.1002/adsc.201800623

  日期：2018.11.5

  A simple and efficient transition metal‐catalyzed C−H amidation with azodicarboxylates has been developed. Under silver catalysis, the amide substrates undergo regioselective C−H amidation at C5‐position of the quinoline. Conversely, with palladium as the catalyst, the reaction gave β‐C(sp3)−H amidation products via the activation of methylene C(sp3)−H bonds. Mechanistic studies suggested that the

  已开发出一种简单有效的过渡金属催化的偶氮二羧酸酯化CH酰胺化反应。在银催化下，酰胺底物在喹啉的C5位发生区域选择性的CH酰胺化。相反，以钯为催化剂，反应通过亚甲基C（sp 3）-H键的活化得到β-C（sp 3）-H酰胺化产物。机理研究表明，单电子转移和有机金属机理途径引起了这些令人惊讶的和截然不同的结果。基于机理分析，我们设计了钯催化/银促进的直接分子间β-C（sp 3）-H酰胺化反应以活化亚甲基C（sp 3）5-氯-8-氨基喹啉（CQ）保护的脂族酰胺与偶氮二羧酸酯的-H键。两种催化方案均提供了替代，便捷和简单的策略，以区域选择性方式有效地访问结构独特的含C N键的化合物。
• Palladium Nanoparticle‐Catalyzed Direct Ethynylation of Aliphatic Carboxylic Acid Derivatives <i>via</i> C( <i>sp</i> ³ )H Bond Functionalization
  作者：Mohammad Al‐Amin、Mitsuhiro Arisawa、Satoshi Shuto、Yusuke Ano、Mamoru Tobisu、Naoto Chatani

  DOI：10.1002/adsc.201301180

  日期：2014.5.5

  We have developed a sulfur‐modified, gold‐supported palladium material (SAuPd) with palladium, Pd, nanoparticles on its surface; it is a recyclable, low‐leaching Pd catalyst. Here we report, using SAuPd, the first example of Pd nanoparticle‐catalyzed, unactivated C(sp3)H bond functionalization of amides, using 8‐aminoquinoline as a directing group, to yield ethynylated products. The low leaching properties

  我们已经开发了一种硫改性的金负载钯材料（SAuPd），其表面具有钯，Pd和纳米颗粒。它是一种可回收，低浸出的Pd催化剂。在这里，我们使用8u-氨基喹啉作为导向基团，使用SAuPd报告了Pd纳米颗粒催化的，未激活的C（sp 3）H键酰胺化官能团的第一个例子，得到了乙炔化产物。SAuPd的低浸出性能使其能够被回收并重复使用10次，以实现C（sp 3）H键功能化。
• Palladium-Catalyzed Cs₂CO₃-Promoted Arylation of Unactivated C(sp³)–H Bonds by (Diacetoxyiodo)arenes: Shifting the Reactivity of (Diacetoxyiodo)arenes from Acetoxylation to Arylation
  作者：Quan Gou、Zhao-Fu Zhang、Zhi-Cheng Liu、Jun Qin

  DOI：10.1021/acs.joc.5b00111

  日期：2015.3.20

  PdCl2(CH3CN)(2)-catalyzed arylation of unactivated C(sp(3))-H bonds using (diacetoxyiodo)arenes as arylation reagents is reported. The reactivity of (diacetoxyiodo)arenes as arylation reagents is enabled in the presence of Cs2CO3 under the reaction conditions. This arylation method is highly efficient and occurs without the use of silver salt. The reaction tolerates a broad substrate scope that was not demonstrated by other silver salt-free C(sp(3))-H bond arylation conditions. The synthetic utility of the method is further illustrated in the synthesis of the psychotropic drug phenibut. A detailed mechanism study has been conducted to understand the reaction pathway.