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

Cryogenic Organometallic Carbon–Fluoride Bond Functionalization with Broad Functional Group Tolerance DOI Creative Commons
D. Lucas Kane, Bryan C. Figula, Kaluvu Balaraman

et al.

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

Published: Feb. 6, 2025

The unique properties of fluorinated organic compounds have received intense interest and conquered a myriad applications in the chemical pharmaceutical sciences. Today, an impressive range alkyl fluorides are commercially available, there many practical methods to make them exist. However, unmatched stability inertness C–F bond largely limited its synthetic value, which is very different from widely accepted utility chlorides, bromides, iodides that serve everyday as "workhorse" building blocks countless carbon–carbon forming reactions. This study demonstrates high-yielding functionalization under mild conditions, i.e., at temperatures low −78 °C, short reaction times with unconventional chemoselectivity. Cryogenic Csp3–F cleavage using fluorophilic organoaluminum together fast nucleophile transfer intermediate ate complexes forge bonds unactivated primary, secondary, tertiary alike. method, exploits Al–F thermodynamic driving force, highly selective toward functionalization, whereas other functional groups including chloride, bromide, iodide, aryl halide, alkenyl, alkynyl, difluoroalkyl, trifluoromethyl, ether, ester, hydroxyl, acetal, heteroaryl, nitrile, nitro, amide tolerated, unexpected reversal long-standing main group organometallic halide cross-coupling reactivity compatibility patterns. As result, strongest single chemistry can now be selectively targeted arylation, alkylation, alkenylation, alkynylation reactions used late-stage complementary currently available methods.

Language: Английский

Citations

0
Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications DOI
Shuai Liu, Jun Zhou, Lu Yu

et al.

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

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

Citations

0
Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides DOI Creative Commons
Hongchao Liu, Xinyu Xu, Siyuan Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871

Published: Jan. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Language: Английский

Citations

3
Nickel-Catalyzed Enantio- and Diastereoselective Synthesis of Fluorine-Containing Vicinal Stereogenic Centers DOI Creative Commons
Uttam Dhawa, Lara Lavrencic, Xile Hu

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 10(8), P. 1657 - 1666

Published: Aug. 17, 2024

The construction of fluorinated architectures has been a topic interest to medicinal chemists due their unique ability improve the pharmacokinetic properties bioactive compounds. However, stereoselective synthesis fluoro-organic compounds with vicinal stereogenic centers is challenge. Herein, we present directing-groupfree nickel-hydride catalyzed hydroalkylation fluoroalkenes afford motifs two adjacent chiral in excellent yields and stereoselectivities. Our method provides expedient access biologically relevant, highly enantioenriched organofluorine Furthermore, strategy can be used for diastereo- enantioselective difluorides, which have recently gained attention fields organocatalysis peptide mimics.

Language: Английский

Citations

2
Enantioselective Synthesis of Alkyl Fluorides via Biocatalytic Reduction DOI Creative Commons
Helen Allan, Yu Wang,

Bethan Winterson

et al.

Published: June 14, 2024

Here we report the first biocatalytic asymmetric synthesis of alkyl fluorides via reduction α-fluoroenones and α-fluoroenoates using ene reductase enzymes. The a wide range (Z) or (E)-α-fluoroenones was shown to proceed in high yield selectivity reductases, with different alkene geometries leading opposite enantiomers chiral fluoroalkane. reaction could also be successfully extended access enantioenriched α-fluoroesters only E-alkene isomers under-going reduction, enabling mixtures employed. substrate scope were rationalized silico substrate-enzyme molecular docking studies.

Language: Английский

Citations

1
Regio- and enantioselective hydrofluorination of internal alkenes via nickel-catalyzed hydrogen atom transfer DOI
Fan Chen, Xiaoyu Zhao,

Weihang Miao

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110239 - 110239

Published: July 1, 2024

Language: Английский

Citations

1
Defluorinative Haloalkylation of Unactivated Alkenes Enabled by Dual Photoredox and Copper Catalysis DOI
Shiyu Li,

Xinguang Li,

Kui-Kui Zhao

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13518 - 13529

Published: Sept. 10, 2024

A three-component defluorinative haloalkylation of alkenes with trifluoromethyl compounds and TBAX (X = Cl, Br) via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array activated aromatics bearing diverse substituents, various nonactivated terminal internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl halides high efficiency. Mechanistic studies indicate that the [Cu] complexes not only serve as XAT catalysts but also facilitate SET reduction groups by photocatalysts. Additionally, resulting alkyl halide products can versatile conversion intermediates for synthesis range compounds.

Language: Английский

Citations

1
Directed Regio- and Enantioselective Hydrofluorination of Alkenes Under Nickel Hydride Catalysis DOI
Martin Oestreich, Hendrik F. T. Klare,

Emilio Acuña Bolomey

et al.

Synfacts, Journal Year: 2024, Volume and Issue: 20(06), P. 0614 - 0614

Published: May 14, 2024

Key words alkenes - asymmetric catalysis hydrofluorination nickel

Language: Английский

Citations

0
Nickel-Catalyzed Regio- and Enantioselective Hydrofluorination in Unactivated Alkenes DOI
Sungwoo Hong, Minseok Kim, Seunghoon Han

et al.

Synlett, Journal Year: 2024, Volume and Issue: 36(02), P. 97 - 102

Published: May 28, 2024

Abstract While enantioselective hydrofluorination methods for activated alkenes represent a notable advance, the resultant enantiomeric excesses remain largely moderate, indicating necessity enhancements in precision, efficiency, and scope. We have recently developed an innovative nickel hydride catalytic system that enables regio- C–F bond formation with unactivated alkenes. By utilizing specially designed Bn-BOx ligands improved selectivity, our approach demonstrates exceptional efficiency selectivity β,γ-alkenyl amide substrates. This breakthrough enhances synthesis of organofluorine compounds, marking significant advancement organic synthesis. 1 Introduction 2 Reaction Design Hydrofluorination 3 Regio- Enantioselective 4 Asymmetric Amplification 5 Conclusions

Language: Английский

Citations

0
Electrooxidative Pd-Catalyzed Remote Hydrofunctionalization of Alkenes with Nucleophiles DOI

Seungdae Park,

Baeho Yang,

Do‐Hyun Lee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15858 - 15868

Published: Oct. 11, 2024

The catalytic hydrofunctionalization of alkenes with nucleophiles via the generation carbocationic intermediates has been extensively studied as an efficient strategy for regioselective installation functional groups on alkene feedstocks. However, since established methods are confined to functionalization position where is originally located, it highly desirable develop a broadly applicable platform that offers alternative regioselectivity otherwise challenging achieve existing protocols. Herein, we report remote method enabled by electrooxidative palladium hydride catalysis. key success formation carbocation intermediate through mechanistic pathway, which involves chain-walking process followed anodic oxidation organopalladium species. This allows terminal and internal broad range oxygen, carbon, nitrogen, fluoride nucleophiles, including complex drug-like molecules.

Language: Английский

Citations

0