Elsevier eBooks, Год журнала: 2023, Номер unknown
Опубликована: Янв. 1, 2023
Язык: Английский
Organic Letters, Год журнала: 2024, Номер 26(24), С. 5098 - 5104
Опубликована: Июнь 7, 2024
We disclose a new general strategy for the site-selective difluoroalkylation of nonprefunctionalized heteroarenes, such as quinoxaline at C-8 position, and benzothiadiazole, benzoxadiazole, benzothiazole C-4 position via consecutive organophotoredox-catalyzed radical–radical cross-coupling base-assisted hydrogen abstraction reactions. The current methodology represents direct difluoroalkylative to allow broad functional group tolerance wide substrate scope in good excellent yields. Careful experimental investigations detailed DFT calculations revealed exact site-selectivity heteroarenes possible mechanistic pathway.
Язык: Английский
Процитировано
4
European Journal of Organic Chemistry, Год журнала: 2025, Номер 28(5)
Опубликована: Янв. 4, 2025
Abstract A stereoselective Ni−Al bimetal‐catalyzed C−H alkenylation of quinazolinones with alkynes has been successfully developed. Good selectivity Z‐type quinazolinone products was obtained using readily available substrates, which exhibits a trans‐configuration opposite to the conventional alkynylation reactions and improves diversity compounds. In addition, reaction process further explored through KIE other control experiments, possible mechanism proposed.
Язык: Английский
Процитировано
0
Chemical Society Reviews, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.
Язык: Английский
Процитировано
0
The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 19, 2025
We report a ruthenium-catalyzed decarboxylative direct mono-2-pyridination of α,β-unsaturated carboxylic acids, offering selective method for synthesizing 2-(1-arylalkenyl)pyridines. Under redox-neutral conditions, the reaction demonstrates broad substrate scope, high functional group tolerance, and significant potential further derivatization. Mechanistic studies reveal that activation allylic C(sp3)-H bond, directed by pyridine group, underpins observed mono-2-pyridination. This work provides an efficient strategy catalytic transformation expanding toolbox functionalizing derivatives.
Язык: Английский
Процитировано
0
Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 29, 2025
Comprehensive Summary Asymmetric cascade Heck/C–H functionalization has emerged as an appealing strategy for activating inert C–H bonds and conveniently synthesizing heterocycles with quaternary centers, owing to the domino sequence of carbopalladation followed by enabling efficient construction multiple in one pot. Herein, a palladium‐catalyzed enantioselective Heck/intermolecular direct heteroarylation reaction unactivated alkenes heteroarenes is developed, providing facile access diverse bis‐heterocycles great practicality bearing all‐carbon stereocenter excellent levels yields enantioselectivities under mild conditions. Moreover, synthetic utility this further demonstrated versatile transformations product.
Язык: Английский
Процитировано
0
ACS Omega, Год журнала: 2025, Номер unknown
Опубликована: Июнь 6, 2025
Язык: Английский
Процитировано
0
Molecular Catalysis, Год журнала: 2023, Номер 552, С. 113673 - 113673
Опубликована: Ноя. 16, 2023
Язык: Английский
Процитировано
6
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(45), С. 31281 - 31294
Опубликована: Окт. 30, 2024
Experimental and theoretical techniques were used to investigate the mechanism of pyridine C–H activation by diarylboryl/bis(phosphine) PBP pincer complexes Ir. The critical intermediate (PBP)IrCO (4) contains a three-coordinate, Ir-bound boron that retains Lewis acidity in perpendicular direction. Coordination this center 4 leads fast insertion Ir into 2-CH bond pyridine, providing different topology direction than conventional directed where both directing group coordination happen at same metal center. Beyond sequence, system possesses significant complexity terms possible isomers pathways, which have been thoroughly explored. Kinetic thermodynamic preferences for differently substituted pyridines also investigated. In experimental work, key is accessed via elimination benzene from phenyl/hydride containing precursor (PBPhP)IrHCO (3). Density functional theory (DFT) investigations loss 3 revealed possibility genuinely new type mechanism, whereby Ph–H made concerted process best described as reductive boron, assisted transition (TMARE). For Ir, pathway was predicted be competitive with more pathways involving but still higher energy barrier. However, Rh analog 3-Rh, TMARE calculated preferred prediction experimentally corroborated through study reaction rates kinetic isotope effect.
Язык: Английский
Процитировано
2
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(3), С. 1505 - 1514
Опубликована: Янв. 13, 2024
The mechanism of the Ni–Al bimetallic-catalyzed C–H cyclization to construct tricyclic imidazoles is investigated using density functional theory calculations. calculation result shows that reaction involves sequential steps substrate coordination, ligand-to-ligand hydrogen transfer (LLHT), and C–C reductive elimination produce final product imidazole. LLHT step calculated be rate-determining step. oxidative addition benzimidazole bond Ni center insertion alkene into Ni–H occur concertedly in effects N-heterocyclic carbene (NHC) ligands AlMe3 on reactivity regioselectivity were also analyzed. These results shed light some ambiguous suggestions from experiments.
Язык: Английский
Процитировано
1
Journal of Catalysis, Год журнала: 2024, Номер 432, С. 115438 - 115438
Опубликована: Март 13, 2024
Язык: Английский
Процитировано
1