Cross‐ and Multi‐Coupling Reactions Using Monofluoroalkanes DOI Creative Commons
Takanori Iwasaki, Nobuaki Kambe

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(9)

Published: April 18, 2023

Abstract Carbon‐fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C−F can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C−C bond formation at monofluorinated sp 3 ‐hybridized carbons via cleavage, including cross‐coupling multi‐component coupling reactions. The cleavage mechanisms the carbon centers primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or nucleophiles supported activation coordination acids; a single electron transfer. characteristic features alkyl fluorides, comparison other (pseudo)halides promising electrophilic counterparts, also discussed.

Language: Английский

Cross-coupling of organic fluorides with allenes: a silyl-radical-relay pathway for the construction of α-alkynyl-substituted all-carbon quaternary centres DOI Creative Commons
Jun Zhou,

Zhengyu Zhao,

Soichiro Mori

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(14), P. 5113 - 5122

Published: Jan. 1, 2024

Cross-coupling of organic fluorides with allenes via radical rearrangement to afford all-carbon quaternary centres mediated by silylboronate/potassium tert -butoxide is disclosed.

Language: Английский

Citations

5
Appealing Renewable Materials in Green Chemistry DOI Creative Commons
Federico Casti, Francesco Basoccu, Rita Mocci

et al.

Molecules, Journal Year: 2022, Volume and Issue: 27(6), P. 1988 - 1988

Published: March 19, 2022

In just a few years, chemists have significantly changed their approach to the synthesis of organic molecules in laboratory and industry. Researchers are encouraged "greener" reagents, solvents, methodologies, go hand with world's environmental matter, such as water, soil, air pollution. The employment plant animal derivates that commonly regarded "waste material" has paved way for development new green strategies. this review, most important innovations field been highlighted, paying due attention those materials played crucial role reactions: wool, silk, feather. Moreover, we decided focus on other supports catalysts syntheses, proteins derivates. Different shown prominent activity adsorption metals dyes, which constituted relevant scope last two decades. We intend furnish complete screening application given these contribute potential future utilization.

Language: Английский

Citations

22
Nickel‐Catalyzed LiCl‐Controlled Switchable Carboxylation of Aryl C—F Bonds with One or Two Molecules of CO2 DOI Open Access

Chunzhe Pei,

Shanglin Han,

Hanxuan Wu

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Comprehensive Summary The use of CO 2 as a renewable C1 source for the synthesis value‐added chemicals can contribute to more sustainable chemistry. In this work, nickel‐catalyzed amide‐directed carboxylation aryl C−F bonds with has been developed. reaction is switchable controlled by LiCl react one or two molecules afford valuable phthalimides α‐hydroxycarboxylic acid derivatives. Further study shows that step‐by‐step process. first step and tandem cyclization phthalimides. second C−N bond , intramolecular nucleophilic addition amide anion carbonyl. also developed based on reaction. work features inert functionalization, activation, multiple incorporation. Mechanistic studies indicate azanickelacycle intermediates play an important role, facilitates reduction Ni(II) Ni(I) promotes molecule . This protocol provides efficient route functionalization under mild conditions via chemical fixation

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
Diastereoselective synthesis of 5,5-Difluoroisoxazolidine via [3 + 2] cycloaddition between Nitrones and Difluoroacrylates DOI
Miaomiao Zhang, Lingyu Kong, Shengqiang Li

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155647 - 155647

Published: May 1, 2025

Language: Английский

Citations

0
Visible-Light-Mediated α-Ketoacylations of NH-Sulfoximines with gem-Difluoroalkenes DOI

Yongliang Tu,

Peng Shi, Carsten Bolm

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(3), P. 907 - 911

Published: Jan. 18, 2022

A photochemical approach for the preparation of α-keto-N-acyl sulfoximines from NH and gem-difluoroalkenes has been developed. In presence NBS, reactions proceed in air without need a photocatalyst or additional oxidant. Results mechanistic studies suggest that two oxygens products stem water dioxygen.

Language: Английский

Citations

16
Nickel-Catalyzed Decarbonylative Reductive Alkylation of Aroyl Fluorides with Alkyl Bromides DOI
Qiang Chen,

Jingwen You,

Tian Tian

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(50), P. 9259 - 9263

Published: Dec. 14, 2022

This paper describes the nickel-catalyzed reductive alkylation of aroyl fluorides with alkyl bromides in a decarbonylative manner. In this reaction, various functional groups are well tolerated and C(sp2)-C(sp3) bond can be constructed directly without use organometallic reagents. The present reaction is cross-electrophile coupling via radical pathway, affording corresponding alkylarenes moderate to good yields.

Language: Английский

Citations

16
Mechanistic Insight into the Ni-Catalyzed Kumada Cross-Coupling: Alkylmagnesium Halide Promotes C–F Bond Activation and Electron-Deficient Metal Center Slows Down β-H Elimination DOI

Yuanyuan Li,

Jun Zhu

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(14), P. 8902 - 8909

Published: June 28, 2022

The Ni-catalyzed Kumada-Tamao-Corriu (KTC) cross-coupling between aryl fluorides and alkyl Grignard reagents has been used to achieve a highly selective Csp2-Csp3 bond construction via the carbon-fluorine (C-F) activation. However, detailed mechanism of this groundbreaking KTC reaction remains unclear. Herein, we perform series analyses by density functional theory (DFT) calculations in order understand mechanisms for activation inert C-F Ni catalysts with bidentate phosphorus ligands. An alternative Ni/Mg bimetallic cooperation cleavage instead traditional oxidative addition was proposed. push-pull interaction transition state provided center Lewis acid Mg cation smoothly breaks bond, supported significantly decreased energy from 30.9 4.6 kcal mol-1 principal interacting orbital analysis. Owing elevated lowest unoccupied molecular level electron-deficient metal caused ligand, β-H elimination could be impeded, increasing selectivity cross-coupling. Our DFT results rationally explain experimental observations, which will helpful further development

Language: Английский

Citations

15
Nickel-catalyzed Suzuki–Miyaura cross-coupling of C–F bonds DOI
Tianhao Zhang,

Itsuki Nohira,

Naoto Chatani

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(14), P. 3783 - 3787

Published: Jan. 1, 2021

The efficient Suzuki–Miyaura cross-coupling of ortho-fluoro aromatic amides with aryl boronates is described. reaction proceeds effectively, even at 60 °C. exhibits a good tolerance for functional groups and broad scope amides.

Language: Английский

Citations

19
Ruthenium-Catalyzed C–F Bond Arylation of Polyfluoroarenes: Polyfluorinated Biaryls by Integrated C–F/C–H Functionalization DOI
Jin Zhang, Jiale Liu, Xiaogang Wang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14337 - 14346

Published: Nov. 7, 2022

Fluorine-containing molecules are central motifs in pharmaceuticals, agrochemicals, and functional materials owing to the unique properties engendered by carbon–fluorine bonds. However, chemoselective synthesis of multifluorinated biaryls, a motif extensively exploited drug discovery, is challenging because difficulty controlling selective fluorination. Herein, we report site-selective arylation C–F bonds polyfluoroarenes enabled ruthenium catalyst system. The present bond proceeds exclusively at ortho-position polyfluorinated arenes through ruthenium(0) chelation readily modifiable directing group. A variety broadly available organoboranes applicable this functionalization, furnishing biaryls featuring removable aldehyde handle. Notably, conditions enable programmed integrated C–F/C–H functionalization same catalyst. This approach characterized broad scope group tolerance build complex biaryls. synthetic utility highlighted ligands, heterocycles, porphyrin analogues. DFT studies provide insight into key selectivity activation. We fully expect that will facilitate implementation defluorination utilizing with high fluorine content.

Language: Английский

Citations

13