The asymmetric -selective hydrogenation of arenes has long been a significant challenge. In this work, we were able to control the / selectivity in ruthenium-catalyzed asymmetric hydrogenation of 2,3-disubstituted quinoxalines by varying the catalyst counteranion. Using density functional theory calculations, we investigated the weak interactions─such as CH/π and hydrogen bonding─among the counteranion, the catalyst framework, and the substrate, elucidating the fundamental influence of counteranions on / selectivity in the asymmetric hydrogenation of quinoxalines.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.5c00458 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ruthenium-Catalyzed Asymmetric -Selective Hydrogenation of 2,3-Disubstituted Quinoxaline Derivatives.
Org Lett
March 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
The asymmetric -selective hydrogenation of arenes has long been a significant challenge. In this work, we were able to control the / selectivity in ruthenium-catalyzed asymmetric hydrogenation of 2,3-disubstituted quinoxalines by varying the catalyst counteranion. Using density functional theory calculations, we investigated the weak interactions─such as CH/π and hydrogen bonding─among the counteranion, the catalyst framework, and the substrate, elucidating the fundamental influence of counteranions on / selectivity in the asymmetric hydrogenation of quinoxalines.
View Article and Find Full Text PDFDirecting Group Enabled Ruthenium-Catalyzed Asymmetric Hydrogenation of Naphthalenes and Related Carbocyclic Aromatics.
Org Lett
February 2025
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China.
Among the aromatic carbocyclic rings, the highly regio- and enantioselective hydrogenation of nonsymmetrical naphthalenes has remained a long-standing challenge in asymmetric catalysis. Herein, we reporte an amide-directed asymmetric hydrogenation of nonsymmetrical naphthalenes with a ruthenium catalyst with up to 99% ee. This strategy was also successfully applied in the asymmetric hydrogenation of polycyclic aromatic hydrocarbons.
View Article and Find Full Text PDFDearomative Addition-Hydrogen Autotransfer for Branch-Selective -Heteroaryl C-H Functionalization via Ruthenium-Catalyzed C-C Couplings of Diene Pronucleophiles.
J Am Chem Soc
January 2025
Department of Chemistry, University of Texas at Austin, Austin 78712, Texas, United States.
Article Synopsis
- A new method for C-H functionalization of heteroaryl compounds is introduced, which involves a process called dearomative addition followed by hydrogen autotransfer.
- This process starts with the hydroruthenation of dienes to create allylruthenium nucleophiles, leading to branched C-C coupling products through addition and β-hydride elimination.
- The study also details the formation of enantiomerically enriched heteroarylethyl alcohols and amines through oxidative cleavage and dynamic kinetic asymmetric reduction, supported by density functional theory calculations linking regioselectivities to molecular factors.
Ruthenium-Catalyzed Carbocycle-Selective Hydrogenation of Fused Heteroarenes.
J Am Chem Soc
December 2024
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
The homogeneous catalytic hydrogenation of benzo-fused heteroarenes generally provides partially hydrogenated products wherein the heteroaryl ring is preferentially reduced, such as quinoline hydrogenation, leading to 1,2,3,4-tetrahydroquinoline. Herein, we report a carbocycle-selective hydrogenation of fused -heteroarenes (quinoline, isoquinoline, quinoxaline, etc.) using the Ru complex of a chiral spiroketal-based diphosphine (SKP) as the catalyst, affording the corresponding 5,6,7,8-tetrahydro products in high chemoselectivities.
View Article and Find Full Text PDFDevelopment of chiral ferrocenyl P,P,N,N,O-ligands for ruthenium-catalyzed asymmetric hydrogenation of ketones.
Org Biomol Chem
December 2024
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Department of Chemistry, and Medi-Pingshan, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen 518055, China.
A new type of ferrocenyl P,P,N,N,O-ligand has been developed through a one-step transformation. This represents a rare example of a ligand containing both chiral bisphosphine and diamine groups suitable for ruthenium-catalyzed asymmetric hydrogenation. Its ruthenium complex can be directly prepared by stirring the ligand and [Ru(benzene)Cl] at 90 °C in DMF for 4 hours.
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!