1-methyl-N-(pivaloyloxy)-1H-indole-2-carboxamide | 1414350-92-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-methyl-N-(pivaloyloxy)-1H-indole-2-carboxamide
• CAS: 1414350-92-7
• 化学式: C₁₅H₁₈N₂O₃
• 分子量: 274.32
• InChiKey: HXUXLFVLQGISGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  20.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  60.33
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  ethynyl MIDA boronate 、 1-methyl-N-(pivaloyloxy)-1H-indole-2-carboxamide 在 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 copper diacetate 、 cesium pivalate 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以91%的产率得到3-(MIDA boronate)-9-methyl-2,9-dihydro-1H-pyrido[3,4-b]indol-1-one
  参考文献：
  名称：

  Mild Rh(III)-Catalyzed C–H Activation and Annulation with Alkyne MIDA Boronates: Short, Efficient Synthesis of Heterocyclic Boronic Acid Derivatives

  摘要：

  Taking advantage of Rh(III)-catalyzed C-H activation reactions, we have developed a mild, short, and efficient method for the synthesis of bench-stable 3-isoquinolone MIDA boronates. The reaction is practical and scalable. The product formed has been applied in the Suzuki-Miyaura reaction with high efficiency. This strategy has also been successfully expanded to the synthesis of MIDA boronate functionalized heterocycles such as isoquinoline, pyrrole, and indole.

  DOI：

  10.1021/ja310153v
• 作为产物：
  描述：

  1-甲基吲哚-2-甲酸 在 草酰氯 、 sodium carbonate 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 生成 1-methyl-N-(pivaloyloxy)-1H-indole-2-carboxamide
  参考文献：
  名称：

  [4 + 2]环化或丢失重排：铑催化发散合成具有抗癌活性的咔啉衍生物

  摘要：

  已经实现了一种不寻常的铑催化的 C–H 活化/Lossen 重排/oxa-Michael 加成串联环化以及众所周知的可调 C–H 活化/[4 + 2] 环化，从而导致区域-、化学-和非对映选择性获得多种五环α-咔啉和β-咔啉-1-酮衍生物，产率中等至良好，具有显着的抗癌活性。

  DOI：

  10.1021/acs.orglett.4c01050

文献信息

• Rhodium(III)-Catalyzed C–H Activation/Annulation with Vinyl Esters as an Acetylene Equivalent
  作者：Nicola J. Webb、Stephen P. Marsden、Steven A. Raw

  DOI：10.1021/ol502095z

  日期：2014.9.19

  The behavior of electron-rich alkenes in rhodium-catalyzed C–H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.

  研究了富电子烯烃在铑催化的CH活化/环化反应中的行为。乙酸乙烯酯以便利的乙炔当量出现，促进了16种3,4-未取代的异喹诺酮以及某些杂芳基稠合的吡啶酮的合成。讨论了烯醇醚相对于烯醇酯/烯酰胺的互补区域化学偏好。
• Regioselective Synthesis of 5-Aminooxazoles via Cp*Co(III)-Catalyzed Formal [3 + 2] Cycloaddition of <i>N</i>-(Pivaloyloxy)amides with Ynamides
  作者：Xiang-Lei Han、Chu-Jun Zhou、Xu-Ge Liu、Shang-Shi Zhang、Honggen Wang、Qingjiang Li

  DOI：10.1021/acs.orglett.7b02959

  日期：2017.11.17

  efficient protocol for the regioselective synthesis of 5-aminooxazoles is disclosed. The reaction, catalyzed by a cheap Cp*Co(III) catalyst, starts from easily accessible N-(pivaloyloxy)amides and ynamides. Mild reaction conditions, a broad substrate scope, good functional group tolerance, and good to excellent yields were observed.

  公开了用于5-氨基恶唑的区域选择性合成的简单有效的方案。该反应由廉价的Cp * Co（III）催化剂催化，从容易获得的N-（新戊酰氧基）酰胺和乙酰胺开始。观察到温和的反应条件，较宽的底物范围，良好的官能团耐受性以及良好的优良产率。
• Rh(III)-Catalyzed Domino [4 + 2] Annulation/Aza-Michael Addition of <i>N</i>-(Pivaloyloxy)benzamides with 1,5-Enynes via C–H Activation: Synthesis of Functionalized Aromathecins
  作者：Chada Raji Reddy、Kathe Mallesh、Srinivas Bodasu、Ramachandra Reddy Donthiri

  DOI：10.1021/acs.joc.0c00615

  日期：2020.6.19

  Reported herein are the Rh(III)-catalyzed cascade annulation reactions of N-(pivaloyloxy)benzamides with 1,5-enynes to access diversely substituted aromathecin derivatives involving C–H activation. The developed procedure offers an efficient synthetic tool for the assembly of a wide range of N-(pivaloyloxy)benzamides and 1,5-enynes with good atom economy and functional group tolerance. The key reactions

  本文报道的是Rh（III）催化的N-（新戊酰氧基）苯甲酰胺与1,5-炔烃的级联环化反应，以得到涉及CH活化的各种取代的芳香族衍生物。所开发的程序为组装具有良好原子经济性和官能团耐受性的各种N-（新戊酰氧基）苯甲酰胺和1,5-烯炔提供了一种有效的合成工具。在无氧化剂温和反应条件下，这种环空反应的关键反应是炔烃插入和氮杂-迈克尔加成反应。
• Rh(III)-Catalyzed C–H Activation/Annulation of Benzohydroxamates and 2-Imidazolones: Access to Urea-Fused-Dihydroisoquinolone Scaffolds Reminiscent of Pyrrole Alkaloid Natural Products
  作者：Grace E. Hubbell、Jetze J. Tepe

  DOI：10.1021/acs.orglett.2c02508

  日期：2022.9.23

  A Rh(III)-catalyzed C–H activation/annulation with an imidazolone as alkene partner is reported to access dihydroisoquinolone-fused imidazolin-2-ones. These bicycles are reminiscent of scaffolds belonging to the pyrrole alkaloid family of natural products. This approach facilitates construction of a variety of urea-fused dihydroisoquinolone scaffolds including heterocyclic moieties.

  据报道，使用咪唑酮作为烯烃伙伴的 Rh(III) 催化的 C-H 活化/环化可以得到二氢异喹诺酮稠合的 imidazolin-2-ones。这些自行车让人想起属于天然产物吡咯生物碱家族的支架。这种方法有利于构建各种脲稠合的二氢异喹诺酮支架，包括杂环部分。
• In Situ Generation of Propadiene from 1-Cyclopropyl-1-nitrosourea for Rh(III)-Catalyzed Synthesis of Isoquinolinones and Pyridinones Containing a Methylene Functionality
  作者：Jintong Bai、Hao Wang、Ting Huang、Jiabing Teng、Ying Song

  DOI：10.1021/acs.orglett.3c00596

  日期：2023.4.28

  pyridinones bearing a methylene motif is presented. This protocol using easily accessible 1-cyclopropyl-1-nitrosourea as the precursor of propadiene features simple and practical manipulation and tolerates a broad spectrum of functional groups, including strong coordinating N-containing heterocyclic substituents. Late stage diversification and the rich reactivity of methylene for further derivations

  介绍了带有亚甲基基序的异喹啉酮和吡啶酮的 Rh(III) 催化合成。该协议使用易于访问的 1-cyclopropyl-1-nitrosourea 作为丙二烯的前体，具有简单实用的操作和容忍广泛的功能组，包括强协调含 N 杂环取代基。后期多样化和亚甲基对进一步衍生的丰富反应性证明了这项工作的价值。