Triplet State‐Promoted Kumada‐Corriu Coupling Catalyzed by Hydrotris(3,5‐diisopropylpyrazolyl)boratocobalt(III)diiodide DOI Creative Commons
Zekun Wang, Yann Cornaton, Jean‐Pierre Djukic

et al.

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(34)

Published: Sept. 4, 2024

Abstract The Kumada‐Corriu hetero‐coupling between an halogeno‐arene and arylmagnesiumbromide can be catalyzed with yields >80 % by the new hydrotris(3,5‐diisopropylpyrazolyl)boratocobalt(III)diiodide, i. e. Tp iPr CoI 2 . catalysis, which is significantly improved upon exposure to light as compared darkness, determined coexistence of low high spin states in a respective ratio ~3 : for crucial “Tp CoAr ” intermediate. pivotal cobalt(I) Co (I) ( thf ) n intermediate shown exclusively triplet state ground measured μ eff value 3.08 B at 293 K C 6 D DFT investigations confirm key role bisaryl‐cobalt(III) intermediates that they provide reaction pathway much lower activation barriers singlet state. low‐to‐high transition THF enhances reactivity intermediate, changes its coordination geometry from 18 electron OC ‐6 16 SPY ‐5 where ligand adopts nearly κ bonding mode. quantitative Independent Gradient Model analysis noncovalent interactions prefigure C−C covalent bond Co(Ar) informs peculiar importance crossover catalysis.

Language: Английский

Synthesis of Fluorinated Compounds by Nickel-Catalyzed Defluorinative Cross-Coupling Reactions DOI

Kuai Wang,

Wangqing Kong

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12238 - 12268

Published: Sept. 1, 2023

Organofluorine compounds have attracted extensive attention in various industrial fields due to their unique chemical and physical properties. Despite increasing demand a wide range of scientific fields, the synthesis organofluorine still faces several problems, such as difficulties handling fluorinating reagents control chemoselectivity. Compared with formation C–F bonds, activation functionalization carbon–fluorine bonds is very important but challenging topic synthetic chemistry. Due properties nickel, Ni-catalyzed defluorinative cross-couplings been greatly developed past few decades powerful strategies for construction fluorinated organic compounds. This Review summarizes advances cross-coupling aryl fluorides, gem-difluorovinyl trifluoromethyl

Language: Английский

Citations

31
Stoichiometric and Catalytic Lithium Nickelate-Mediated C–F Bond Alkynylation of Fluoroarenes DOI
Andryj M. Borys, Luca Vedani, Eva Hevia

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10199 - 10205

Published: March 28, 2024

Low-valent nickelates have recently been shown to be key intermediates that facilitate challenging cross-coupling reactions under mild conditions. Expanding the synthetic potential of these heterobimetallic complexes, herein we report success trilithium nickelate Li3(TMEDA)3Ni(C≡C–Ph)3 in promoting stoichiometric C–F activation assorted aryl fluorides furnishing novel mixed Li/Ni(0) or Li/Ni(II) species depending on substrate and conditions employed. These successes can upgraded catalytic regimes enable atom-efficient alkynylation polyfluoroarenes with lithium acetylides precatalyst Ni(COD)2, which operates without intervention external ligands, Cu cocatalysts, additives.

Language: Английский

Citations

8
Elucidating the Key Factors in Hydroamination and Defluoroamination Competitions: A DFT Analysis of Reaction between α‐(Trifluoromethyl)styrene and 2‐Pyridones DOI
Haoran Xu, Yuchen Zhang, Xiao‐Song Xue

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(17)

Published: April 3, 2024

Abstract β ‐fluorocarbanions have garnered considerable attention for their dual reactivity in nucleophilic processes and ‐fluorine elimination. In this study, a thorough computational analysis was conducted to explore the reactions of α ‐(trifluoromethyl)styrenes with 2‐pyridones delineate factors determining protonation or defluorination pathways situ generated under varied basic conditions. Our findings illuminate critical role organobase basicity steering direction competitive elimination reactions. We propose use p K aH values organobases as quantitative indicator discerning predominant reaction pathways. This provides an efficient approach predict control outcome, facilitating deliberate design leverage unique realm fluorine chemistry.

Language: Английский

Citations

4
Axially Chiral Bridged Biaryls by Ni-Catalyzed Kinetic Asymmetric C–O Bond Cleavage DOI
Yijun Fang,

Jiameng Hu,

Tingting Sun

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8176 - 8183

Published: May 10, 2024

Axially chiral bridged biaryls represent an important subset of axially biaryl scaffolds in fields ranging from organic synthesis to biochemistry materials science. While numerous catalytic strategies have been elucidated for the construction axial chirality, enantioenriched form remains underdeveloped. Herein, we demonstrate approach synthesize diverse through nickel-catalyzed kinetic asymmetric cleavage unactivated aromatic C–O bond. The system features mild reaction conditions, high resolution efficiency, and versatile post-functionalizations. Mechanistic studies reveal impact nickel catalyst's chirality on stereochemical output this transformation.

Language: Английский

Citations

4
Magnesium Nickelate Complexes and Their Implications in Ni-Catalyzed Cross-Couplings of Aryl Fluorides and Aryl Ethers with Grignard Reagents DOI
Luca Vedani, Andryj M. Borys, Eva Hevia

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 12, 2025

The nickel-catalyzed Kumada-Tamao-Corriu cross-coupling reaction is widely used to form C-C bonds and receives continued interest due the unique ability of nickel activate challenging organic electrophiles containing C-F C-O bonds. Recent studies on Ar-F Ar-OMe with organolithium nucleophiles have unveiled key involvement highly reactive anionic nickelates, in which Li Ni cooperatively promote activation these substrates. However, possible formation related heterobimetallic intermediates when employing organomagnesium as partners still remains underexplored. Filling this gap knowledge, we use air-stable Ni-tris(olefin), Ni(4-Me-stb)3 (where stb = stilbene), a Ni(0) precursor systematically investigate its reactivity toward several reagents, has allowed for structural spectroscopic characterization new family nickelate complexes. Their implications influence their constitution speciation outcome cross-couplings are also investigated through series stoichiometric catalytic reactions, uncovered dramatic solvent effect, hinting at contacted ion pair species maximizing Mg (or Li)/Ni(0) cooperativity.

Language: Английский

Citations

0
Heterolytic Bond Dissociation Energy Related to C−F Activation in Nickel-Catalyzed Cross-Coupling of Phenylmagnesium Chloride with Fluoroarenes DOI
Hongli Wu,

Junjie Tai,

Jialun Xu

et al.

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 123674 - 123674

Published: April 1, 2025

Language: Английский

Citations

0
Dialumene as a Dimeric or Monomeric Al Synthon for C–F Activation in Monofluorobenzene DOI Creative Commons

Xufang Liu,

Shicheng Dong, Jun Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23591 - 23597

Published: Aug. 6, 2024

The activation of C-F bonds has long been regarded as the subject research in organometallic chemistry, given their synthetic relevance and fact that fluorine is most abundant halogen Earth's crust. However, bond remains a largely unsolved challenge due to high dissociation energies, which was historically dominated by transition metal complexes. Main group elements can cleave unactivated monofluorobenzene are still quite rare restricted s-block complexes with biphilic nature. Herein, we demonstrate an Al-mediated using neutral dialumene, allowing for synthesis formal oxidative addition products at either double or single aluminum centers. This dialumene system introduces novel methodology based on reductive elimination processes around two centers, demonstrated combined experimental computational studies. A "masked" alumylene unprecedentedly synthesized prove proposed pathway. Furthermore, utility highlighted functionalization resulting aryl-aluminum compounds.

Language: Английский

Citations

2
Mechanistic study of nickel-catalyzed intramolecular [4 + 2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect DOI
Jinxia Li,

Jinbo Luo,

Wen‐Yan Tong

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1134 - 1146

Published: Jan. 1, 2023

The transition metal catalyzed cycloaddition reaction is one of the most powerful tools for construction carbon- and heterocycles. DFT studies are performed to investigate mechanism Ni-catalyzed intramolecular [4 + 2] cycloaddition.

Language: Английский

Citations

6
C–F bond functionalizations via fluorinated carbenes DOI

Yingmei Li,

Jiangbin Luo, Yaojia Jiang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(22), P. 5782 - 5804

Published: Jan. 1, 2023

This feature article summarizes the developments in fluorinated carbene transformations, and their consequent C–F functionalization a cascade platform.

Language: Английский

Citations

5
Understanding the Reaction Mechanism of Nickel-Catalyzed Enantioselective Arylative Activation of the Aromatic C–O Bond DOI
Xin Xu, Zhenyang Lin

Organometallics, Journal Year: 2022, Volume and Issue: 42(1), P. 114 - 122

Published: Dec. 21, 2022

Mild synthetic methods to transform aromatic carbon–oxygen (C–O) bonds into useful molecules have great potential in renewable biomass conversion. Recently, a Ni–NHC (N-heterocyclic carbene) complex catalyzing an asymmetric ring-opening reaction of dinaphthofuran with PhMgCl at room temperature was reported. In this work, we carried out density functional theory (DFT) calculations investigate the detailed mechanism. The DFT results reveal novel mechanism that involves Mg(II)–O coordination followed by migration phenyl nucleophile Ni(0) metal center prior oxidative addition C–O bond Ni(0). Insights how chiral NHC ligand helps induce enantioselectivity been obtained.

Language: Английский

Citations

6