quinolin-2-yl N,N-diethyl-O-carbamate | 117902-17-7

• 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: quinolin-2-yl N,N-diethyl-O-carbamate
• 英文别名: N,N-diethyl O-(quinolyl-2) carbamate；quinolin-2-yl diethylcarbamate；Carbamic acid, diethyl-, 2-quinolinyl ester；quinolin-2-yl N,N-diethylcarbamate
• CAS: 117902-17-7
• 化学式: C₁₄H₁₆N₂O₂
• 分子量: 244.293
• InChiKey: NIPVCUUMACEMII-UHFFFAOYSA-N

物化性质

• 沸点：
  378.6±24.0 °C(Predicted)
• 密度：
  1.156±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  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：
  0.29
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  quinolin-2-yl N,N-diethyl-O-carbamate 在 C₄₃H₆₀ClFeNNiP₂ 、 氨 、 sodium t-butanolate 作用下， 以 1,4-二氧六环 、 邻二甲苯 为溶剂， 反应 16.0h， 以36%的产率得到2-氨基喹啉
  参考文献：
  名称：

  氨基甲酸芳基酯与氨的镍催化胺化

  摘要：

  氨基甲酸芳基酯用于氨的镍催化单芳基化。应用的、定义明确的单组分镍 (II) 预催化剂包含 Josiphos 配体，在空气中稳定，并且无需任何辅助还原剂即可运行。该催化剂体系还促进了氨基甲酸芳基酯与硫酸铵以及伯烷基胺的盐酸盐的胺化。它们的容易制备、稳健性和导向基团能力使氨基甲酸芳基酯成为特别有吸引力的合成中间体。

  DOI：

  10.1002/ejoc.201700660
• 作为产物：
  描述：

  2-喹啉醇 、 N,N-二乙基氯甲酰胺 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以88%的产率得到quinolin-2-yl N,N-diethyl-O-carbamate
  参考文献：
  名称：

  定向金属结合/交叉偶联联合策略：抗肿瘤药喜树碱的四环A / B / C / D环核的合成

  摘要：

  描述了使用定向原位金属化和Negishi交叉偶联的组合喜树碱的A / B / C / D环片段5的会聚合成。合成序列的关键特征是阴离子邻位-弗里斯重排（10 → 12），Negishi交叉偶联（7 → 6）和末端修饰的von Braun反应（16 → 5），导致四环衍生物5在7个步骤，总收率11％。

  DOI：

  10.1021/jo049890h

文献信息

• Revisitation of Organoaluminum Reagents Affords a Versatile Protocol for C–X (X = N, O, F) Bond-Cleavage Cross-Coupling: A Systematic Study
  作者：Hiroyuki Ogawa、Ze-Kun Yang、Hiroki Minami、Kumiko Kojima、Tatsuo Saito、Chao Wang、Masanobu Uchiyama

  DOI：10.1021/acscatal.7b01058

  日期：2017.6.2

  A revisit of organoaluminum reagents for cross-coupling reactions has opened up several types of C–C bond formation protocols through cleavage of phenolic/alcoholic C–O and C–F and ammonium C–N bonds. Catalyzed by the commercially available NiCl2(PCy3)2 catalyst, these reactions proceed smoothly with a wide range of substrates and broad functional group compatibility, providing a versatile methodology

  再次探讨用于交叉偶联反应的有机铝试剂，通过裂解酚/醇C-O和C-F和铵C-N键，开辟了几种类型的C-C键形成规程。在市售的NiCl 2（PCy 3）2催化剂的催化下，这些反应可在多种底物和广泛的官能团相容性下顺利进行，从而为有机铝介导的交叉偶联过程提供了一种通用的方法。
• <i>N</i>,<i>N-</i>Diethyl <i>O-</i>Carbamate: Directed Metalation Group and Orthogonal Suzuki−Miyaura Cross-Coupling Partner
  作者：Aurora Antoft-Finch、Tom Blackburn、Victor Snieckus

  DOI：10.1021/ja907700e

  日期：2009.12.16

  was established to be a crucial parameter for this transformation. When combined with DoM and traditional Pd-catalyzed Suzuki-Miyaura strategies, the methodology offers concise routes to uniquely substituted molecules, avoiding the need for protection/deprotection of the phenol and the use of strongly nucleophilic cross-coupling partners.

  首次 Suzuki-Miyaura 交叉偶联芳基 O-氨基甲酸酯是定向邻位金属化 (DoM) 化学中的一种多功能且强大的定向金属化基团 (DMG)，使用廉价、长期稳定的催化剂 NiCl(2)(PCy) 进行描述(3))(2)。芳基和杂芳基 O-氨基甲酸酯具有广泛的合成范围和良好的效率。水和游离硼酸和环硼氧烷之间的水解平衡的作用被确定为这一转化的关键参数。当与 DoM 和传统 Pd 催化的 Suzuki-Miyaura 策略相结合时，该方法为独特的取代分子提供了简洁的途径，避免了对苯酚的保护/脱保护和使用强亲核交叉偶联伙伴的需要。
• DFT Studies Provide Mechanistic Insight into Nickel-Catalyzed Cross-Coupling Involving Organoaluminum-Mediated C–O Bond Cleavage
  作者：Chao Wang、Masanobu Uchiyama、Ze-Kun Yang

  DOI：10.1055/s-0036-1590863

  日期：2017.12

  Density functional theory (DFT) calculations were performed to examine the reaction pathway of Ni-catalyzed cross-coupling with organoaluminum through C–O bond cleavage. The results indicate that the strong Lewis acidity of organoaluminums significantly facilitates the transmetalation step, but not the oxidative addition or reductive elimination step.

  进行密度泛函理论 (DFT) 计算以检查 Ni 催化通过 C-O 键裂解与有机铝交叉偶联的反应途径。结果表明，有机铝的强路易斯酸性显着促进了金属转移步骤，但不利于氧化加成或还原消除步骤。
• Nickel-Catalyzed Suzuki–Miyaura Couplings in Green Solvents
  作者：Stephen D. Ramgren、Liana Hie、Yuxuan Ye、Neil K. Garg

  DOI：10.1021/ol401727y

  日期：2013.8.2

  The nickel-catalyzed Suzuki-Miyaura coupling of aryl halides and phenol-derived substrates with aryl boronic acids using green solvents, such as 2-Me-THF and tert-amyl alcohol, is reported. This methodology employs the commercially available and air-stable precatalyst, NiCl2(PCy3)(2), and gives biaryl products in synthetically useful to excellent yields. Using this protocol, bis(heterocyclic) frameworks can be assembled efficiently.
• Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies
  作者：Kyle W. Quasdorf、Aurora Antoft-Finch、Peng Liu、Amanda L. Silberstein、Anna Komaromi、Tom Blackburn、Stephen D. Ramgren、K. N. Houk、Victor Snieckus、Neil K. Garg

  DOI：10.1021/ja200398c

  日期：2011.4.27

  The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)(2) to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.