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

Nickel-Catalyzed Direct Cross-Coupling of Aryl Thioether with Aryl Bromide DOI
Nana Ma,

Xuan-Bo Hu,

Yuan-Shuai Wu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(10), P. 1771 - 1775

Published: March 2, 2023

A straightforward cross-coupling of aryl thioether with bromide the aid nickel salt, magnesium, and lithium chloride in tetrahydrofuran at ambient temperature was accomplished. The one-pot reactions proceeded efficiently via C-S bond cleavage to produce desired biaryls modest good yields, avoiding use pregenerated or commercial organometallic reagents.

Language: Английский

Citations

35
Nickel-catalyzed cross-electrophile coupling of aryl thiols with aryl bromides via C–S bond activation DOI

Hao Xu,

Cai-Yu He,

Bo‐Jie Huo

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(20), P. 5171 - 5179

Published: Jan. 1, 2023

We report a cross-electrophile coupling of aryl thiols with bromides via C–S bond activation instead S–H cleavage. The reaction proceeded effectively in the presence nickel catalyst, magnesium, and lithium chloride to afford various biaryls moderate good yields.

Language: Английский

Citations

25
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

Citations

13
Nickel-catalyzed cross-electrophile coupling of unactivated (hetero)aryl sulfone with aryl bromide DOI
Wenxin Li,

Bo‐Jie Huo,

Jie-Ying Huang

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 430, P. 115359 - 115359

Published: Feb. 1, 2024

Language: Английский

Citations

10
Direct Cross-Couplings of Aryl Nonaflates with Aryl Bromides under Nickel Catalysis DOI
Hao Xu,

Jia-Wen Jing,

Yubing Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

The direct cross-couplings of aryl nonaflates with bromides could be successfully accomplished by utilizing nickel as the catalyst, magnesium metal mediator, and lithium chloride additive. reactions proceeded efficiently in THF at room temperature to produce desired biaryls moderate good yields, showing both a reasonable substrate scope functional group tolerance. Additionally, an equally performance realized when reaction was subjected scale-up synthesis. Preliminary study suggested that presumably proceeds through situ formation arylmagnesium reagent key intermediate.

Language: Английский

Citations

1
The Directing Group: A Tool for Efficient and Selective C–F Bond Activation DOI
Amrita Das, Naoto Chatani

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 12915 - 12930

Published: Oct. 8, 2021

C–F bond activation is currently considered to be "a hot topic" in many different but interconnected fields of research, due its inherent inertness and unique properties. While considerable progress has been made this particular field activating strong bonds, such as the bond, continues a challenge. Because polyfluorinated compounds are commercially available, functionalization bonds extensively studied for preparing partially fluorinated compounds, some which biologically active used functionalized materials. However, chemo- regioselective methods still required prepare useful compounds. In addition, new strategy less reactive monofluorinated remains need. Directed strategies have C–H chemistry achieve high efficiency well regioselectivity. On other hand, directed that applicable various unreactive C–O, C–N, C–F, others needed, compared with activation. Review, we focus on inert bonds.

Language: Английский

Citations

50
A General, Multimetallic Cross-Ullmann Biheteroaryl Synthesis from Heteroaryl Halides and Heteroaryl Triflates DOI
Kai Kang, Nathan L. Loud, Tarah A. DiBenedetto

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(51), P. 21484 - 21491

Published: Dec. 17, 2021

Despite their importance to medicine and materials science, the synthesis of biheteroaryls by cross-coupling remains challenging. We describe here a new, general approach biheteroaryls: Ni- Pd-catalyzed multimetallic cross-Ullmann coupling heteroaryl halides with triflates. An array 5-membered, 6-membered, fused bromides chlorides, as well aryl triflates derived from heterocyclic phenols, proved be viable substrates in this reaction (62 examples, 63 ± 17% average yield). The generality was further demonstrated 96-well plate format at 10 μmol scale. 96 possible products provided >90% hit rate under single set conditions. Further, low-yielding combinations could rapidly optimized "Toolbox Plate" ligands, additives, reductants.

Language: Английский

Citations

50
The Anionic Pathway in the Nickel‐Catalysed Cross‐Coupling of Aryl Ethers DOI Creative Commons
Andryj M. Borys, Eva Hevia

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(46), P. 24659 - 24667

Published: Sept. 1, 2021

The Ni-catalysed cross-coupling of aryl ethers is a powerful method to forge new C-C and C-heteroatom bonds. However, the inert C(sp2 )-O bond means that canonical mechanism relies on oxidative addition ether Ni0 centre thermodynamically kinetically unfavourable, which suggests alternative mechanisms may be involved. Here, we provide spectroscopic structural insights into anionic pathway, formation electron-rich hetero-bimetallic nickelates by adding organometallic nucleophiles centre. Assessing rich co-complexation chemistry between Ni(COD)2 PhLi has led structures solution-state diverse family catalytically competent lithium being unveiled. In addition, demonstrate dramatic solvent donor effects, suggest cooperative activation substrate -ate complexes plays key role in catalytic cycle.

Language: Английский

Citations

47
Nickel-Catalyzed Reductive Cross-Coupling of Heteroaryl Chlorides and Aryl Chlorides DOI
Bijan Mirabi, Austin D. Marchese, Mark Lautens

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(20), P. 12785 - 12793

Published: Oct. 6, 2021

We report a nickel-catalyzed cross-electrophile coupling reaction of aryl chlorides and heteroaryl enabled by synergistic combination consisting halide effects the addition magnesium salt. The relies on electronic difference between aromatic heteroaromatic partners to afford cross-coupled biaryl products using single catalyst. A variety heterocycles were amenable reaction, as well wide range chlorides, with electron-deficient performing best in reaction. Preliminary mechanistic evidence demonstrates MgCl2 is essential accelerating reduction Ni(II), that small quantities iodide lead improved yields.

Language: Английский

Citations

46
Nickel-Catalyzed Direct Cross-Coupling of Unactivated Aryl Fluorides with Aryl Bromides DOI

Jing‐Ao Ren,

Jin-He Na,

Chao Gui

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(29), P. 5525 - 5529

Published: July 17, 2023

A nickel-catalyzed direct cross-coupling of unactivated aryl fluorides with bromides is realized. The one-pot reaction, which avoids the use preformed and sensitive organometallic reagents, proceeds effectively via C-F bond cleavage at room temperature in THF presence phosphine ligand magnesium powder (with or without TMSCl) to produce desired biaryls modest good yields.

Language: Английский

Citations

19