On the Existence and Relevance of Copper(III) Fluorides in Oxidative Trifluoromethylation DOI
Noel Nebra, Daniel Joven‐Sancho

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: June 24, 2024

Abstract Numerous reports invoke CuIII–F intermediates engaging in oxidative cross-couplings mediated by low/mid-valent copper and formal sources of ‘F+’ oxidants. These elusive typically instable CuIII fluorides have been rarely characterized or spectroscopically identified, making their existence participation within catalytic cycles somehow questionable. We authenticated a stable organocopper(III) fluoride that undergoes Csp–CF3 bond formation upon addition silyl-capped alkynes following 2 e– CuIII/CuI redox shuttle. This finding strongly supports the intermediacy C–C coupling. review herein state art about well-defined enabling cross-coupling reactions. 1 Introduction Brief History Coupling-Competent Fluorides 3 Design an Isolable – yet Reactive Organocopper(III) Fluoride 4 Alkyne Trifluoromethylation: Scope Mechanism 5 Extension to Aryl–CF3 C–Heteroatom Couplings 6 Summary Outlook

Language: Английский

Intercepting Ketone α-Arylation Intermediates in the DalPhos/Ni-Catalyzed Synthesis of Decorated Benzofurans and NH-Indoles DOI

Joshua W. M. MacMillan,

Katherine N. Robertson, Mark Stradiotto

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3751 - 3767

Published: Feb. 17, 2025

Language: Английский

Citations

0
New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes DOI
Shenghan Teng,

Peiyao Liang,

Jianrong Steve Zhou

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Language: Английский

Citations

0
Nickel-Catalyzed Asymmetric Homobenzylic Hydroamidation of Aryl Alkenes to Access Chiral β-Arylamides DOI
Xiang Lyu,

Eunmi Jeon,

Changhyeon Seo

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in synthesis β-(hetero)arylethylamides. By employing transposed NiH catalysis approach, this method facilitates formation key chiral nickel-amido intermediates, enabling insertion into alkenes to produce desired β-arylamide products with excellent enantioselectivity. The exhibits high functional group tolerance utilizes readily available starting materials vinylarenes react dioxazolone as robust amidating source. Notably, approach was successfully applied pharmaceutical compounds natural products, such Clobenzorex, Direx, Selegiline, Sacubitril, Cipargamin.

Language: Английский

Citations

0
Soft Copper Nanoimprinting via Solid-State Electrochemical Etching for Flexible Optoelectronics DOI

Atsuki Tsuji,

Taizo Kobayashi,

Junji Murata

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Patterned Cu is widely used for various electronic components, including metal interconnects. In the optoelectronic industry, high-resolution nanopatterning of surfaces commonly performed via photolithography, which requires photoresists and harsh chemicals. this study, we developed a method fabricating nanopatterns based on solid-state electrochemical etching at interface between polymer electrolyte membrane (PEM) Cu. The reaction selectively ionized surface in contact with patterned PEM stamp, allowing direct patterning without using resists or This approach was successfully applied to produce patterns resolutions less than 100 nm hierarchical structures. Such subwavelength scale (several hundred nanometers) enable miniaturization electrical circuits tuning optical transmission/reflection spectra enhance device surfaces. Semitransparent electrodes fabricated nanopatterned poly(ethylene terephthalate) films exhibited good transmission resistance properties. proposed stamp-based technique avoids need liquid electrolytes resists, thereby offering simple, low-cost, environmentally friendly process

Language: Английский

Citations

0
Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents DOI Creative Commons
Qianqian Chang,

Qini Li,

Yi-Hui Deng

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 3, 2025

Language: Английский

Citations

0
In Situ Stm Study of Ni-Modified Pt(111) Electrodes: Structural Evolution and Hydrogen Evolution Activity in Koh DOI
Shuehlin Yau, Chao‐Lin Chung

Published: Jan. 1, 2025

Language: Английский

Citations

0
The Development of Cage Phosphine ‘DalPhos’ Ligands to Enable Nickel-Catalyzed Cross-Couplings of (Hetero)aryl Electrophiles DOI Creative Commons

Kathleen M. Morrison,

Mark Stradiotto

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7394 - 7407

Published: Jan. 1, 2024

The development of the DalPhos cage ligand family and application in developing state-of-the-art nickel-catalyzed cross-coupling chemistry is described.

Language: Английский

Citations

3
Overcoming Electron Bias in Hydroarylation of Phenylpropiolic Acid Derivatives To Enable Highly Reversed Regio- and Stereoselectivity via Steric and Transient Post Addition Coordination DOI
Hui Li, Xu Tian,

Qin-Qin Dang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(13), P. 9985 - 9992

Published: June 19, 2024

The regio- and stereoselective hydroarylation of internal alkynes via transition-metal catalysis offers a direct approach for designing highly stereodefined multifunctionalized olefins. Through recognition electronic bias, β-syn-hydroarylation poor with arylboronic acids has been well studied. However, from the same starting materials, achieving opposite α-selective anti-stereoselective remains significant challenge due to these inherent biases. Therefore, an alternative synthetic pathway trisubstituted alkenes reversed positioning configuration substituents is desirable. Based on steric repulsion-induced regioselectivity transient post-addition coordination-directed stereoselectivity, we report herein α-hydroarylation method phenylpropiolic esters using nickel catalyst that promotes formal anti-addition pathway. A broad range organoboronic acid derivatives are compatible this protocol, offering selectivity traditional reactions. distinct advantages our include precise control over selectivity, reduced loading, tolerance toward functional groups. These features highlight potential in synthesis late-stage modification alkyne-based drug intermediates, showcasing its versatility applicability organic synthesis.

Language: Английский

Citations

3
Ni-catalysed remote C(sp3)–H functionalization using chain-walking strategies DOI
Ciro Romano, Rubén Martı́n

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

3
An Organocopper(III) Fluoride Triggering C−CF3 Bond Formation DOI Creative Commons
Daniel Joven‐Sancho, Andrea Echeverri, Nathalie Saffon‐Merceron

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(11)

Published: Dec. 26, 2023

Abstract Copper(III) fluorides are catalytically competent, yet elusive, intermediates in cross‐coupling. The synthesis of [PPh 4 ][Cu III (CF 3 ) F] ( 2 ), the first stable (isolable) Cu −F, was accomplished via chloride addition to [Cu (py)] 1 yielding Cl(py)] ⋅Cl), followed by treatment with AgF. halides ⋅Cl and were fully characterized using nuclear magnetic resonance (NMR) spectroscopy, single crystal X‐ray diffraction (Sc‐XRD) elemental analysis (EA). Complex proved capable forging C−CF bonds from silyl‐capped alkynes. In‐depth mechanistic studies combining probes, theoretical calculations, trapping intermediate a ([PPh (C≡CPh)]) radical tests unveil key role acetylides that undergo facile e − reductive elimination furnishing trifluoromethylated alkynes (RC≡CCF which industrially relevant synthons drug discovery, pharma agrochemistry.

Language: Английский

Citations

9