Nonheme Mononuclear and Dinuclear Iron(II) and Iron(III) Fluoride Complexes and Their Fluorine Radical Transfer Reactivity DOI
Vishal Yadav, Lyupeng Wen, Sudha Yadav

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 682 - 691

Published: Dec. 27, 2024

The nonheme iron(II) complexes containing a fluoride anion, FeII(BNPAPh2O)(F) (1) and [FeII(BNPAPh2OH)(F)(THF)](BF4) (2), were synthesized structurally characterized. Addition of dioxygen to either 1 or 2 led the formation fluoride-bridged, dinuclear iron(III) complex [Fe2III(BNPAPh2O)2(F)2(μ-F)]+ (4), which was characterized by single-crystal X-ray diffraction, 1H NMR, elemental analysis. An iron(II)(iodide) complex, FeII(BNPAPh2O)(I) (3), prepared reacted with O2 give mononuclear cis-FeIII(BNPAPh2O)(OH)(I) (5). excess 5 oxo-bridged, [Fe2III(BNPAPh2O)2(F)2(μ-O)] (6), while iron(III)(fluoride) cis-FeIII(BNPAPh2O)(F)(Cl) (7) from addition F– FeIII(BNPAPh2O)Cl2. 4 6 unreactive fluorine radical transfer, but 7 reacts substrate (p-MeO-C6H4)3C• transfer products FeII(BNPAPh2O)(Cl) (p-OMe-C6H4)3CF. These results show that FeIII(F) is capable mediating even in presence second coordination sphere hydrogen bonds ligand. findings are placed context what known about iron halogenases related synthetic catalysts regarding their ability, lack thereof, mediate reactions.

Language: Английский

Engineering non-haem iron enzymes for enantioselective C(sp3)–F bond formation via radical fluorine transfer DOI
Qun Zhao, Zhenhong Chen, Jordi Soler Soler

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(8), P. 958 - 966

Published: March 28, 2024

Language: Английский

Citations

25
Transition-metal-catalyzed C(sp3)–H bond fluorination reactions DOI

Robbie Ge,

Ziting Xu, Ke Yang

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(7), P. 101009 - 101009

Published: June 6, 2024

Language: Английский

Citations

8
Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C–H Functionalization DOI
Isaac M. Blythe, Jingtong Xu, J. Scott O'Dell

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18253 - 18259

Published: Aug. 8, 2023

Over the past decade, numerous reports have focused on development and applications of Cu-mediated C-H functionalization reactions; however, to date, little is known about Cu intermediates involved in these transformations. This paper details observation characterization CuII CuIII aminoquinoline-directed C(sp2)-H a fluoroarene substrate. An initial activation at occurs room temperature afford an isolable anionic cyclometalated complex. complex undergoes single-electron oxidation with ferrocenium or AgI salts under mild conditions (5 min temperature) C(sp2)-C(sp2) C(sp2)-NO2 coupling products. Spectroscopic studies implicate formation transient diamagnetic CuIII-σ-aryl intermediate that either (i) second followed by C-C bond-forming reductive elimination (ii) reaction NO2- nucleophile coupling.

Language: Английский

Citations

14
Synthesis, Characterization, and Reactivity of a Highly Oxidative Mononuclear Manganese(IV)–Bis(Fluoro) Complex DOI
Donghyun Jeong,

Yujeong Lee,

Yuri Lee

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4172 - 4177

Published: Feb. 5, 2024

Recently, transition-metal terminal nonoxo complexes have shown a remarkable ability to activate and functionalize C–H bonds via proton-coupled electron transfer (PCET). Here we report the first example of mononuclear manganese(IV) bis(fluoro) complex bearing tetradentate pyridinophane ligand, [MnIV(TBDAP)(F)2]2+ (3), with an X-ray single crystal structure physicochemical characterization. The has very high reduction potential 1.61 V vs SCE, thereby enabling four-electron oxidation mesitylene 3,5-dimethylbenzaldehyde. Kinetic studies, including kinetic isotope effect employment other toluene derivatives, reveal (ET)-driven PCET in bond activation by 3. This novel metal halide intermediate would be prominently valuable for expanding chemistry.

Language: Английский

Citations

5
Copper–oxygen adducts: new trends in characterization and properties towards C–H activation DOI Creative Commons
Jonathan De Tovar, Rébecca Leblay, Yongxing Wang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(27), P. 10308 - 10349

Published: Jan. 1, 2024

Recent progresses in Cu–oxygen adducts towards recalcitrant C–H activation are reviewed with focus on Cu metalloenzymes and bioinspired synthetic models, mono- to polynuclear complexes, working under homogeneous heterogeneous catalytic conditions.

Language: Английский

Citations

5
Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation DOI Creative Commons

Luca Demonti,

Daniel Joven‐Sancho, Noel Nebra

et al.

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

Published: June 20, 2023

Abstract Ag III compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement catalysts in cross‐coupling via 2 e − redox sequences is frequently discarded. Nevertheless, organosilver(III) have been authenticated using tetradentate macrocycles or per fluorinated groups as supporting ligands, and since 2014, first examples enabled by I /Ag cycles saw light. This review collects most relevant contributions to this field, with main focus on aromatic fluorination/ fluoroalkylation identification key intermediates. Pertinent comparison between activity R F aryl‐F aryl‐CF 3 couplings vs. one shown its Cu Au congeners herein disclosed, thus providing a more profound picture scope these transformations pathways commonly associated C−R bond formations coinage metals.

Language: Английский

Citations

10
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
Pt/IrOx enables selective electrochemical C-H chlorination at high current DOI Creative Commons
Bo Wu, Ruihu Lu, Chao Wu

et al.

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

Published: Jan. 2, 2025

Employing electrochemistry for the selective functionalization of liquid alkanes allows sustainable and efficient production high-value chemicals. However, large potentials required C(sp3)-H bond low water solubility such make it challenging. Here we discover that a Pt/IrOx electrocatalyst with optimized Cl binding energy enables generation free radicals C-H chlorination alkanes. For instance, achieve monochlorination cyclohexane current up to 5 A, Faradaic efficiency (FE) 95% stable performance over 100 h in aqueous KCl electrolyte. We further demonstrate our system can directly utilize concentrated seawater derived from solar evaporation reverse osmosis process, achieving FE 93.8% towards chlorocyclohexane at 1 A. By coupling photovoltaic module, showcase solar-driven using membrane electrode assembly cell without any external bias. Our findings constitute pathway renewable driven chemicals manufacture abundant feedstock industrially relevant rates. Large activation electrochemical Here, authors report

Language: Английский

Citations

0
Site-Selective C(sp3)–H Fluorination of Saccharides: Switching the Reaction Sites by Changing Fluorination Reagents and Hydrogen Atom Transfer Catalysts DOI

Erina Kurokawa,

Yanru Li,

S. Okuyama

et al.

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

Published: May 31, 2025

We successfully developed a method for the site-selective C(sp3)-H fluorination of saccharides. When saccharides were treated with Selectfluor under 405 nm light irradiation, selectively proceeded at weakest bond. Conversely, when same N-fluorobenzenesulfonimide in presence sodium decatungstate catalyst 365 reaction site could be switched and occurred bond less steric hindrance.

Language: Английский

Citations

0
Alkyl Fluoride Synthesis via Cu-Mediated Deacetylative Fluorination DOI

Zining Zhang,

Kezhi Chen,

Peng Liu

et al.

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

Published: June 3, 2025

Given the increasing demand for diverse alkyl fluorides various applications, it would be beneficial to enrich fluorination toolbox by including more kinds of common functional groups, such as ketones, fluoride surrogates. Here we report a Cu-mediated deacylative approach that can convert wide range methyl ketones corresponding fluorides. The reaction is enabled ketone activation reagent and nucleophilic source. It features broad group tolerance, capability late-stage fluorination, fluoro-annulation, synthesis α,α-dideuterated fluorides, degree-controlled mono-, di-, trifluoro alkanes from single starting material. computational studies suggest interesting Cu(III)-mediated C-F bond forming pathways via either fluorine atom transfer or an SN2 process.

Language: Английский

Citations

0