Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Pd-Catalyzed C–H Arylation DOI Creative Commons
Jonathan Galicia, Nicholas McDonald,

Christopher Bennett

et al.

Published: Nov. 22, 2023

While photocatalysts are generally responsible for radical generation from bench stable diaryliodonium salts, recent reports have emerged exhibiting photocatalyst-free using select Lewis bases as activators. Herein, we demonstrate 1) the ability of numerous to enable light-driven and 2) these radicals can be captured by transition-metals coupling reactions. These results first step toward developing new organometallic aryl reactions without photocatalysts.

Language: Английский

Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Metal-Catalyzed C–H Arylation DOI
Jonathan Galicia, Nicholas McDonald,

Christopher Bennett

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(54), P. 6929 - 6932

Published: Jan. 1, 2024

We demonstrate (1) detectable halogen bonding is not critical for enabling light-driven radical generation from diaryliodonium salts and (2) radicals generated by this route can be captured transition-metals C-H arylation reactions. These results are the first step toward developing new metal-catalyzed aryl couplings without exogenous photocatalysts.

Language: Английский

Citations

1
Triphenylphosphine Oxide: A Versatile Covalent Functionality for Carbon Nanotubes DOI Creative Commons
Yanlin Pan, Dominika Baster,

Daniel Käch

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 1, 2024

Abstract Broadening the scope of functionalities that can be covalently bound to single‐walled carbon nanotubes (SWCNTs) is crucial for enhancing versatility this promising nanomaterial class in applied settings. Here we report covalent linkage triphenylphosphine oxide [Ph 3 P(O)] SWCNTs, a hitherto overlooked surface functionality. We detail synthesis and structural characterization new family phosphine oxide‐functionalized diaryliodonium salts facilitate direct Ph P(O) transfer afford novel SWCNTs with tunable content ( SWCNT‐P ). The molecularly‐distributed robust nature attachment was supported by combination methods including Raman, infrared, UV/Vis‐NIR X‐ray photoelectron spectroscopies coupled thermogravimetric analysis. Electron microscopy further revealed effectiveness moiety de‐bundling yield superior dispersibility processability. Finally, electrochemical studies established sensitive presence Li + , Na K wherein Gutmann‐Beckett Lewis acidity parameters ions were quantitatively transduced responses. This work hence presents synthetic, structural, spectroscopic foundation phosphorus‐enriched responsive platform featuring

Language: Английский

Citations

1
Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Pd-Catalyzed C–H Arylation DOI Creative Commons
Jonathan Galicia, Nicholas McDonald,

Christopher Bennett

et al.

Published: Nov. 21, 2023

Diaryliodonium salts are bench stable aryl radical precursors. While photocatalysts generally responsible for generation, recent reports have emerged exhibiting photocatalyst-free generation using select Lewis bases as activators. Herein, we demonstrate 1) the ability of numerous to enable light-driven and 2) these radicals can be captured by transition-metals coupling reactions. These results first step toward developing new organometallic reactions without photocatalysts.

Language: Английский

Citations

1
Triphenylphosphine Oxide: A Versatile Covalent Functionality for Carbon Nanotubes DOI Creative Commons
Yanlin Pan, Dominika Baster,

Daniel Käch

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: Aug. 1, 2024

Abstract Broadening the scope of functionalities that can be covalently bound to single‐walled carbon nanotubes (SWCNTs) is crucial for enhancing versatility this promising nanomaterial class in applied settings. Here we report covalent linkage triphenylphosphine oxide [Ph 3 P(O)] SWCNTs, a hitherto overlooked surface functionality. We detail synthesis and structural characterization new family phosphine oxide‐functionalized diaryliodonium salts facilitate direct Ph P(O) transfer afford novel SWCNTs with tunable content ( SWCNT‐P ). The molecularly‐distributed robust nature attachment was supported by combination methods including Raman, infrared, UV/Vis‐NIR X‐ray photoelectron spectroscopies coupled thermogravimetric analysis. Electron microscopy further revealed effectiveness moiety de‐bundling yield superior dispersibility processability. Finally, electrochemical studies established sensitive presence Li + , Na K wherein Gutmann‐Beckett Lewis acidity parameters ions were quantitatively transduced responses. This work hence presents synthetic, structural, spectroscopic foundation phosphorus‐enriched responsive platform featuring

Language: Английский

Citations

0
Arylation of Secondary Phosphines with Diaryliodonium Salts under Metal‐Free and Non‐Photochemical Conditions DOI
Ajit Kumar Jha, Sudeep Sarkar, Kacper Szczepanski

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract A metal‐ and irradiation‐free approach for the direct arylation of secondary phosphines has been developed. The reaction employs diaryliodonium salts as electrophilic aryl‐transfer reagents, effecting P−Ar bond‐formation in a single step, under mild conditions, using t ‐BuOK base DMSO solvent. protocol furnishes expedient access to diverse unsymmetrical triarylphosphines and, upon one‐pot oxidation, corresponding triarylphosphine oxides. Experimental computational studies support inner sphere mechanism through reductive coupling at hypervalent iodine center. calculations also point key role played by potassium ions, providing extra stabilization P−C bond‐forming transition state binding reactants via cation‐π interactions.

Language: Английский

Citations

0
Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Pd-Catalyzed C–H Arylation DOI Creative Commons
Jonathan Galicia, Nicholas McDonald,

Christopher Bennett

et al.

Published: Nov. 22, 2023

While photocatalysts are generally responsible for radical generation from bench stable diaryliodonium salts, recent reports have emerged exhibiting photocatalyst-free using select Lewis bases as activators. Herein, we demonstrate 1) the ability of numerous to enable light-driven and 2) these radicals can be captured by transition-metals coupling reactions. These results first step toward developing new organometallic aryl reactions without photocatalysts.

Language: Английский

Citations

0