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

Photoinduced Vicinal Difunctionalization of Diaryliodonium Salts To Access Bis(tetraphenylphosphonium) Salts DOI
Yu Wang, Limin Wang, Jianwei Han

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 1012 - 1017

Published: Jan. 21, 2025

Vicinal bis(tetraarylphosphonium) salts have scarcely been reported in the literature. In this study, we demonstrate that visible-light-induced difunctionalization of ortho-trifluoromethylsulfonylated diaryliodonium conveniently furnishes bis(phosphonium) without additional catalysts or photoinitiators. The methodology establishes a practical platform for preparation using readily available tertiary phosphines. are anticipated to garner great deal interest catalytic and medicinal chemistry.

Language: Английский

Citations

0
Electron donor–acceptor complex photoactivation for deaminative alkynylation, alkenylation and allenylation: a comprehensive study DOI
Romain Lapierre,

Lina Truong,

Matthieu Hédouin

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(8), P. 2231 - 2240

Published: Jan. 1, 2024

Herein, we disclose our study toward photoinduced deaminative alkynylation, alkenylation and allenylation.

Language: Английский

Citations

2
IGMH‐based research on the intramolecular weak interaction of TKX‐50 DOI
Chunhai Yang, Huilong Dong, Xue Li

et al.

Propellants Explosives Pyrotechnics, Journal Year: 2024, Volume and Issue: 49(3)

Published: March 1, 2024

Abstract To further comprehensively study the intramolecular weak interaction of gaseous TKX‐50 molecule, two conformations molecule were analyzed via Independent Gradient Model based on Hirshfeld Partition (IGMH) method B3LYP/6‐311 g (d,p) level for geometry optimization and single point energy. The conclusions manifest that interactions between these fragments are mainly composed hydrogen bonds van der Waals interactions. From strength inter‐fragment formed by contributing atomic pairs their percentage contributions, H bonds, together with dispersion‐dominated provided non‐direct facing near dominate resulting in stability molecular structure. Meanwhile, enclosed end‐atoms not only include contributions but also intra‐fragment fragment 1. For conformation II, due to transfer fragments, a pair symmetric at corresponding regions extremely strong reach covalent bond while groups −OH other end become looser, II own lower Differences essentially brought stronger electron‐withdrawing ability atom O than N.

Language: Английский

Citations

2
Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Metal-Catalyzed C–H Arylation DOI Creative Commons
Jonathan Galicia, Nicholas McDonald,

Christopher Bennett

et al.

Published: March 20, 2024

Herein, we demonstrate 1) that Lewis base heteroatom coordination to diaryliodonium salts is not required for light-driven radical generation and 2) radicals generated by this route can be captured transition-metals coupling reactions. These results are the first step toward developing new aryl reactions without exogenous photocatalysts.

Language: Английский

Citations

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

Christopher Bennett

et al.

Published: May 15, 2024

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

Language: Английский

Citations

1
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
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