Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Silver-catalyzed late-stage fluorination.

ABSTRACT: Carbon-fluorine bond formation by transition metal catalysis is difficult, and only a few methods for the synthesis of aryl fluorides have been developed. All reported transition-metal-catalyzed fluorination reactions for the synthesis of functionalized arenes are based on palladium. Here we present silver catalysis for carbon-fluorine bond formation. Our report is the first example of the use of the transition metal silver to form carbon-heteroatom bonds by cross-coupling catalysis. The functional group tolerance and substrate scope presented here have not been demonstrated for any other fluorination reaction to date.

SUBMITTER: Tang P

PROVIDER: S-EPMC2935811 | biostudies-literature | 2010 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Silver-catalyzed late-stage fluorination.

Tang Pingping P Furuya Takeru T Ritter Tobias T

Journal of the American Chemical Society 20100901 34

Carbon-fluorine bond formation by transition metal catalysis is difficult, and only a few methods for the synthesis of aryl fluorides have been developed. All reported transition-metal-catalyzed fluorination reactions for the synthesis of functionalized arenes are based on palladium. Here we present silver catalysis for carbon-fluorine bond formation. Our report is the first example of the use of the transition metal silver to form carbon-heteroatom bonds by cross-coupling catalysis. The functio ...[more]

PMID: 20695434

Similar Datasets

Silver-catalyzed vinylogous fluorination of vinyl diazoacetates.

Project description:A silver-catalyzed vinylogous fluorination of vinyl diazoacetates to generate γ-fluoro-α,β-unsaturated carbonyls is presented. Application of this method to the fluorination of farnesol and steroid derivatives was achieved.

| S-EPMC3880583 | biostudies-literature

Late-Stage Fluorination: From Fundamentals to Application.

Project description:In this brief account, we review work from our lab with a focus on late-stage introduction of fluorine and fluorinated functional groups into small molecules. We attempt to highlight practical developments, which we believe may have potential for industrial applications, and critically reflect on developments that may not yet meet the bar for practical use.

| S-EPMC4372057 | biostudies-other

A fluoride-derived electrophilic late-stage fluorination reagent for PET imaging.

Project description:The unnatural isotope fluorine-18 ((18)F) is used as a positron emitter in molecular imaging. Currently, many potentially useful (18)F-labeled probe molecules are inaccessible for imaging because no fluorination chemistry is available to make them. The 110-minute half-life of (18)F requires rapid syntheses for which [(18)F]fluoride is the preferred source of fluorine because of its practical access and suitable isotope enrichment. However, conventional [(18)F]fluoride chemistry has been limited to nucleophilic fluorination reactions. We report the development of a palladium-based electrophilic fluorination reagent derived from fluoride and its application to the synthesis of aromatic (18)F-labeled molecules via late-stage fluorination. Late-stage fluorination enables the synthesis of conventionally unavailable positron emission tomography (PET) tracers for anticipated applications in pharmaceutical development as well as preclinical and clinical PET imaging.

| S-EPMC3229297 | biostudies-literature

Site-Selective Late-Stage Aromatic [18 F]Fluorination via Aryl Sulfonium Salts.

Project description:Site-selective functionalization of C-H bonds in small complex molecules is a long-standing challenge in organic chemistry. Herein, we report a broadly applicable and site-selective aromatic C-H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two-step C-H [18 F]fluorination of a series of marketed small-molecule drugs.

| S-EPMC7004179 | biostudies-literature

Late-stage [<sup>18</sup>F]Fluorination: New Solutions to Old Problems.

Project description:The last 2-3 years have seen numerous relationships develop between organometallic chemists, fluorine chemists and PET Centers around the world. These collaborations have led to the development of many new strategies for the late-stage introduction of fluorine-18 into complex bioactive molecules. In this perspective we highlight recent developments and key milestones since 2011.

| S-EPMC4217215 | biostudies-literature

Silver-mediated fluorination of aryl silanes.

Project description:A regiospecific silver-mediated fluorination of aryl silanes is reported. The reaction is operationally simple, and employs Ag(2)O as readily available, inexpensive silver source, which can be recovered.

| S-EPMC3117666 | biostudies-literature

Copper-Catalyzed Electrochemical C-H Fluorination.

Project description:We report the systematic development of an electrooxidative methodology that translates stoichiometric C-H fluorination reactivity of an isolable CuIII fluoride complex into a catalytic process. The critical challenges of electrocatalysis with a highly reactive CuIII species were addressed by the judicious selection of electrolyte, F- source, and sacrificial electron acceptor. Catalyst-controlled C-H fluorination occurs with a preference for hydridic C-H bonds with high bond dissociation energies over weaker but less hydridic C-H bonds. The selectivity is driven by an oxidative asynchronous proton-coupled elelctron transfer (PCET) at an electrophilic CuIII-F complex. We further demonstrate that the asynchronicity factor of hydrogen atom transfer η can be used as a guideline to rationalize the selectivity of C-H fluorination.

| S-EPMC9894310 | biostudies-literature

Synthesis and late-stage functionalization of complex molecules through C-H fluorination and nucleophilic aromatic substitution.

Project description:We report the late-stage functionalization of multisubstituted pyridines and diazines at the position α to nitrogen. By this process, a series of functional groups and substituents bound to the ring through nitrogen, oxygen, sulfur, or carbon are installed. This functionalization is accomplished by a combination of fluorination and nucleophilic aromatic substitution of the installed fluoride. A diverse array of functionalities can be installed because of the mild reaction conditions revealed for nucleophilic aromatic substitutions (S(N)Ar) of the 2-fluoroheteroarenes. An evaluation of the rates for substitution versus the rates for competitive processes provides a framework for planning this functionalization sequence. This process is illustrated by the modification of a series of medicinally important compounds, as well as the increase in efficiency of synthesis of several existing pharmaceuticals.

| S-EPMC4227713 | biostudies-literature

Palladium-Catalyzed Nondirected Late-Stage C-H Deuteration of Arenes.

Project description:We describe a palladium-catalyzed nondirected late-stage deuteration of arenes. Key aspects include the use of D2O as a convenient and easily available deuterium source and the discovery of highly active N,N-bidentate ligands containing an N-acylsulfonamide group. The reported protocol enables high degrees of deuterium incorporation via a reversible C-H activation step and features extraordinary functional group tolerance, allowing for the deuteration of complex substrates. This is exemplified by the late-stage isotopic labeling of various pharmaceutically relevant motifs and related scaffolds. We expect that this method, among other applications, will prove useful as a tool in drug development processes and for mechanistic studies.

| S-EPMC8517979 | biostudies-literature

Efficient palladium-catalyzed electrocarboxylation enables late-stage carbon isotope labelling

Project description: Not available

| S-EPMC10959938 | biostudies-literature