A Single‐Atom Cobalt Catalyst for the Fluorination of Acyl Chlorides at Parts‐per‐Million Catalyst Loading DOI
Wenhao Li,

Bo‐Chao Ye,

Jiarui Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 24, 2022

Improving the stability of sensitive catalytic systems is an emerging research topic in catalysis field. However, current design heterogeneous catalysts mainly improves their performance. This paper presents a single-atom catalyst (SAC) strategy to improve cobalt-catalysed fluorination acyl chlorides. A stable Co-F intermediate can be formed through oxidative Co1 -N4 @NC SAC, which replace unstable high-valent cobalt system and avoid use phosphine ligands. In SAC system, KF employed as fluorinating reagent AgF, applied various substrates scale-up conversion with high turnover numbers (TON=1.58×106 ). work also shows that inorganic SACs have tremendous potential for organofluorine chemistry, it provides good reference follow-up studies on structure-activity relationship between chemical reaction mechanisms.

Language: Английский

Electrochemical strategies for C–H functionalization and C–N bond formation DOI Creative Commons
Markus D. Kärkäs

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(15), P. 5786 - 5865

Published: Jan. 1, 2018

This review provides an overview of the use electrochemistry as appealing platform for expediting carbon–hydrogen functionalization and carbon–nitrogen bond formation.

Language: Английский

Citations

880

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration DOI Creative Commons
Luca Capaldo, Davide Ravelli, Maurizio Fagnoni

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Language: Английский

Citations

801

Modern Approaches for Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs DOI
Yi Zhu, Jianlin Han, Jiandong Wang

et al.

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(7), P. 3887 - 3964

Published: April 2, 2018

New methods for preparation of tailor-made fluorine-containing compounds are in extremely high demand nearly every sector chemical industry. The asymmetric construction quaternary C-F stereogenic centers is the most synthetically challenging and, consequently, least developed area research. As a reflection this apparent methodological deficit, pharmaceutical drugs featuring constitute less than 1% all medicines currently on market or clinical development. Here we provide comprehensive review current research activity area, including such general directions as electrophilic fluorination via organocatalytic and transition-metal catalyzed reactions, elaboration substrates alkylations, Mannich, Michael, aldol additions, cross-coupling biocatalytic approaches.

Language: Английский

Citations

572

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons DOI
Odile Eisenstein,

Jessica Milani,

Robin N. Perutz

et al.

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8710 - 8753

Published: June 27, 2017

Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal lanthanide systems. Although the C-H bond is weaker than C-F regardless hybridization carbon, reaction at usually more exothermic corresponding bonds. Both bonds are activated systems, but preference for activating these depends on nature hydrocarbon system, so that directed exclusively toward or yield mixture products. Additionally, presence fluorine differentiates between different positions resulting in regioselective activation; paradoxically, strongest reacts preferentially. The purpose this review to describe field reactions partially substrates with atoms, ions, molecular complexes. controlling physical properties (thermodynamics kinetics) described first, followed description stoichiometric reactions, competition activations as focus. A few representative catalytic systems discussed. also highlights benefit combining experimental theoretical studies.

Language: Английский

Citations

290

New Horizons of Photocatalytic Fluoromethylative Difunctionalization of Alkenes DOI Creative Commons
Takashi Koike, Munetaka Akita

Chem, Journal Year: 2017, Volume and Issue: 4(3), P. 409 - 437

Published: Dec. 21, 2017

Language: Английский

Citations

257

Deoxyfluorination with Sulfonyl Fluorides: Navigating Reaction Space with Machine Learning DOI

Matthew K. Nielsen,

Derek T. Ahneman,

Orestes Riera

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(15), P. 5004 - 5008

Published: March 27, 2018

Through fine-tuning of reagent and base structure, sulfonyl fluorides can efficiently fluorinate diverse classes alcohols. We show that machine learning map the intricate reaction landscape enable accurate prediction high-yielding conditions for untested substrates.

Language: Английский

Citations

234

Contemporary synthetic strategies in organofluorine chemistry DOI
Robert Britton, Véronique Gouverneur, Jin‐Hong Lin

et al.

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: July 8, 2021

Language: Английский

Citations

212

Where Does the Fluorine Come From? A Review on the Challenges Associated with the Synthesis of Organofluorine Compounds DOI
Stéphane Caron

Organic Process Research & Development, Journal Year: 2020, Volume and Issue: 24(4), P. 470 - 480

Published: March 5, 2020

Fluorinated organic molecules are increasingly being prepared for a variety of applications, including pharmaceutical products. However, the supply chain to access necessary raw materials, which originate primarily from calcium fluoride, is often not considered, may be difficult at commercial scale, and has become destabilized as more stringent environmental policies justifiably enforced. This manuscript presents an overview preparation use simple organofluorinated intermediates reagents challenges associated with them.

Language: Английский

Citations

202

Strategies for Nucleophilic C(sp3)–(Radio)Fluorination DOI
Isabelle Nathalie-Marie Leibler, Shivaani Gandhi, Makeda A. Tekle‐Smith

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9928 - 9950

Published: April 24, 2023

This Perspective surveys the progress and current limitations of nucleophilic fluorination methodologies. Despite long rich history C(sp3)–F bond construction in chemical research, inherent challenges associated with this transformation have largely constrained to a privileged reaction platform. In recent years, Doyle group─along many others─has pursued study development intent generating deeper mechanistic understanding, developing user-friendly reagents, contributing invention synthetic methods capable enabling radiofluorination. Studies from our laboratory are discussed along developments others field. Fluoride reagent implications identity highlighted. We also outline space inaccessible by technologies series future directions field that can potentially fill existing dark spaces.

Language: Английский

Citations

51

The Role of Small Molecules Containing Fluorine Atoms in Medicine and Imaging Applications DOI Creative Commons

Emily Henary,

Stefanie Casa, Tyler L. Dost

et al.

Pharmaceuticals, Journal Year: 2024, Volume and Issue: 17(3), P. 281 - 281

Published: Feb. 22, 2024

The fluorine atom possesses many intrinsic properties that can be beneficial when incorporated into small molecules. These include the atom’s size, electronegativity, and ability to block metabolic oxidation sites. Substituents feature fluorine-containing groups are currently prevalent in drugs lower cholesterol, relieve asthma, treat anxiety disorders, as well improve chemical of various medications imaging agents. dye scaffolds (fluorescein/rhodamine, coumarin, BODIPY, carbocyanine, squaraine dyes) reported will address incorporation scaffold contribution it provides its application an agent. It is also important recognize radiolabeled atoms used for PET early detection diseases. This review discuss benefits incorporating molecules give examples fluorinated pharmaceutical industry techniques.

Language: Английский

Citations

19