AI Article Synopsis
- Researchers developed a simple method to create various -(CH-aryl/alkyl)-substituted -(pyridin-2-yl)benzamides using palladium to activate C(sp)-H bonds.
- A key intermediate, dinuclear palladacycle, was characterized using techniques like mass spectrometry and X-ray crystallography.
- The process demonstrated good versatility with functional groups and included a successful conversion of the produced compounds into -(CH-aryl)-2-aminopyridine.
Article Abstract
Herein, we present a facile synthetic methodology to produce a range of -(CH-aryl/alkyl)-substituted -(pyridin-2-yl)benzamides via palladium-mediated C(sp)-H bond activation. The -methyl--(pyridin-2-yl)benzamide precursor was first reacted with palladium(II) acetate in a stoichiometric manner to obtain the key dinuclear palladacycle intermediates, whose structures were elucidated by mass spectrometric, NMR spectroscopic, and X-ray crystallographic studies in detail. The subsequent C(sp)-H bond functionalizations on the -methyl group of the starting substrate show facile productions of the corresponding -(CH-aryl/alkyl)-substituted -(pyridin-2-yl)benzamides with good functional group tolerance. A plausible mechanism was proposed based on density functional theory calculations in conjunction with kinetic isotope effect experiments. Finally, the synthetic transformation from the prepared -(CH-aryl)--(pyridin-2-yl)benzamides through debenzoylation to -(CH-aryl)-2-aminopyridine was successfully demonstrated.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.3c00429 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Palladium Iodide Catalyzed Multicomponent Carbonylative Synthesis of 2-(4-Acylfuran-2-yl)acetamides.
Molecules
September 2023
Laboratory of Industrial and Synthetic Organic Chemistry (LISOC), Department of Chemistry and Chemical Technologies, University of Calabria, Via Pietro Bucci 12/C, 87036 Arcavacata di Rende, Italy.
2-Propargyl-1,3-dicarbonyl compounds have been carbonylated under oxidative conditions and with the catalysis of the PdI/KI catalytic system to selectively afford previously unreported 2-(4-acylfuran-2-yl)acetamides in fair to good yields (54-81%) over 19 examples. The process takes place under relatively mild conditions and occurs via a mechanistic pathway involving C-H activation by oxidative monoamincarbonylation of the terminal triple bond of the substrates with formation of 2-ynamide intermediates, followed by 5---cyclization (via intramolecular conjugate addition of the in situ formed enolate to the 2-ynamide moiety) and aromative isomerization.
View Article and Find Full Text PDFRecent progress in the oxidative coupling of unactivated Csp-H bonds with other C-H bonds.
Chem Commun (Camb)
December 2021
Department of Chemistry, Fudan University, 2005 Songhu Rd, Shanghai, 200438, China.
Article Synopsis
- - The article discusses the oxidative coupling of carbon-hydrogen (C-H) bonds as a simple and efficient way to create carbon-carbon (C-C) bonds from hydrocarbons without needing any prior modifications.
- - It highlights recent advancements in coupling unactivated Csp-H bonds with various hybrid C-H bonds, including combinations with Csp-H bonds.
- - The paper provides a summary of the types of substrates used, proposed reaction mechanisms, and potential applications, aiming to inspire new methods for building Csp-C bonds effectively.
Metal-Catalyzed Decarboxylative C-H Functionalization.
Chem Rev
July 2017
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, China.
Article Synopsis
- C-H bond activation and decarboxylation are important techniques in organic synthesis, leading to a new method called decarboxylative C-H bond functionalization.! -
- This review highlights recent advancements in utilizing this method to synthesize various organic compounds, including styrenes, chalcones, and heterocycles.! -
- The article discusses the effectiveness, limitations, and potential applications of decarboxylative functionalization across different types of C-H bonds.!
Synthesis of bicyclic p-diiodobenzenes via silver-catalyzed Csp-H iodination and ruthenium-catalyzed cycloaddition.
J Am Chem Soc
June 2006
Department of Applied Chemistry Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan.
Highly substituted iodobenzenes were efficiently and regioselectively synthesized from readily available 1,6-diynes via two-step process consisting of silver-catalyzed Csp-H iodination and subsequent ruthenium-catalyzed [2 + 2 + 2] cycloaddition of resultant iododiynes. Some of the obtained iodobenzenes were subjected to palladium-catalyzed C-C bond-forming reactions such as Mizoroki-Heck reaction, Sonogashira reaction, and Suzuki-Miyaura coupling, giving highly conjugated molecules.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!