A protocol for the Pd(II)-catalyzed C-H alkenylation reaction of substituted -allylanilines via an unusual 6- process has been developed. A density functional theory (DFT) study of the mechanistic pathway has shown that the coordination of the remote protecting group to the palladium center is determinant for the control of the regioselectivity in favor of the 6- process. The reaction would proceed via prior activation of the alkene. This procedure constitutes a mild and efficient method for the synthesis of 1,4-dihydroquinoline derivatives from simple and readily accessible substrates.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.9b03174 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cobalt(II)-Catalyzed Selective C2-H Heck Reaction of Native (N-H) Indoles Enabled by Salicylaldehyde Ligand.
J Org Chem
January 2025
Collaborative Innovation Center for Advanced Organic Chemical Materials Co-Constructed by the Province and Ministry, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
Direct functionalization of native (N-H) indoles via C-H activation remains a challenge. Herein, we report a salicylaldehyde-promoted cobalt-catalyzed selective C2-H Heck reaction of native (N-H) indoles with both active and unactivated olefins in the presence of free N-H bonds. A series of structurally diverse C2-alkenylated native (N-H) indoles including natural product and drug derivatives were prepared directly and effectively without additional preprotection and deprotection procedures.
View Article and Find Full Text PDFRu(II)-Catalyzed -Vinylation of Benzoic Acids in Water.
J Org Chem
January 2025
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur 302017, Rajasthan, India.
Article Synopsis
- A new method for the oxidative C-H alkenylation of benzoic acid using [Ru(η-CH)Cl] catalyst has been developed, operating efficiently in water at mild temperatures (60 °C).
- The reaction shows regioselectivity, producing mono-olefinated products when using activated alkenes like acrylates, while both mono and diolefinated products emerge from unactivated alkenes such as styrene.
- A novel five-membered cyclic compound was formed from vinylferrocene as a coupling partner, indicating a unique reactivity profile compared to other alkenes.
Salicylaldehyde-Enabled Co(II)-Catalyzed Oxidative C-H Alkenylation of Indoles with Olefins.
J Org Chem
January 2025
Collaborative Innovation Center for Advanced Organic Chemical Materials Co-constructed by the Province and Ministry, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules. Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals. College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
A ligand-promoted oxidative dehydrogenation C-H alkenylation of indoles and olefins was achieved using commercial and low-cost Co(NO)·6HO as a catalyst and Mn(OAc) as an oxidant. The design and selection of electrically unique methyl-substituted salicylaldehyde as a ligand is the key to achieve this transformation. This protocol can introduce an indole backbone into diverse bioactive molecules such as ibuprofen, naproxen, and Estrol for late-stage synthetic modification, which has potential applications in the discovery of drug molecules containing an indole motif.
View Article and Find Full Text PDFSynthesis of Tetracyclic-Fused Dihydroindeno[2,1-]chromenes via Palladium-Catalyzed Alkyne Insertion and C-H Bond Activation.
J Org Chem
January 2025
Jiangsu Key Laboratory for Chemistry of Low Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, China.
An unprecedented Pd-catalyzed cascade alkyne insertion/Heck/C-H activation reaction of -iodophenyl alkenyl ethers and diarylacetylenes has been developed. Diversified tetracyclic-fused dihydroindeno[2,1-]chromenes bearing a quaternary center were constructed in an efficient, straightforward, and atom-economic way with good to excellent yields. The protocol features high bonding efficiency, operational simplicity, broad substrate scope, and easy scale-up.
View Article and Find Full Text PDFHeteroaryl-Directed Iridium-Catalyzed Enantioselective C-H Alkenylations of Secondary Alcohols.
J Am Chem Soc
January 2025
Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom.
Under iridium-catalyzed conditions, 2-aza-aryl-substituted secondary alcohols undergo C(sp)-H addition reactions to alkynes to provide alkenylated tertiary alcohols. The processes occur with very high regio- and enantioselectivity. An analogous addition to styrene is shown to provide a prototype C(sp)-H alkylation process.
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!