Activation and C‒C Coupling of Aryl Iodides via Bismuth Photocatalysis DOI Creative Commons
Mauro Mato, Alexios Stamoulis, Paolo Cleto Bruzzese

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Abstract Within the emerging field of bismuth redox catalysis, catalytic formation C−C bonds using aryl halides would be highly desirable; yet such a process remains synthetic challenge. Herein, we present chemoselective bismuth‐photocatalyzed activation and subsequent coupling (hetero)aryl iodides with pyrrole derivatives to access C(sp 2 )−C(sp ) linkages through C−H functionalization. This unique reactivity is result complex featuring two state‐dependent interactions light, which 1) activates Bi(I) for oxidative addition via MLCT, 2) promotes homolytic cleavage Bi(III) intermediates LLCT process.

Language: Английский

Recent advances in heavier Group 15 (P, As, Sb, Bi) radical chemistry – frameworks, small molecule reactivity, and catalysis DOI Creative Commons

Deana L. G. Symes,

Jason D. Masuda

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

New developments in the area of heavier pnictogen-based radicals continue to be reported, along with small molecule reactivity and newly discovered catalytic reactions.

Language: Английский

Citations

0
Visible Light‐Induced Arylation/Alkylation/Phosphorylation of Isocyanides viaEDA Complex Activation DOI Open Access

Shichao Yang,

Xiangwen Tan,

Dan Liu

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Comprehensive Summary Herein, it is reported that the aryl radicals derived from thianthrenium salts are used as coupling partner in arylation reactions of isocyanides, simultaneously initiators for formation alkyl and phosphoryl ethers diarylphosphine oxides. This cascade cyclization reaction leads to diverse arylated, alkylated phosphorylated heteroaromatic compounds. Notably, this transformation can be achieved without aid metals or photocatalysts, exhibiting a wide substrate applicability operational simplicity. Mechanistic studies suggest involvement radical processes electron donor‐acceptor (EDA) complexes transformation.

Language: Английский

Citations

0
Transition metal-free difunctionalization of unactivated alkenes: Arylation/azidation, arylation/chlorination, and arylation/cyanation DOI
Li Li, Viresh H. Rawal

Chem, Journal Year: 2024, Volume and Issue: 10(10), P. 3243 - 3253

Published: Sept. 2, 2024

Language: Английский

Citations

3
Activation and C‒C Coupling of Aryl Iodides via Bismuth Photocatalysis DOI Creative Commons
Mauro Mato, Alexios Stamoulis, Paolo Cleto Bruzzese

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Within the emerging field of bismuth redox catalysis, catalytic formation C-C bonds using aryl halides would be highly desirable; yet such a process remains synthetic challenge. Herein, we present chemoselective bismuth-photocatalyzed activation and subsequent coupling (hetero)aryl iodides with pyrrole derivatives to access C(sp

Language: Английский

Citations

2
Precatalyst Evolution in PBiP-Pd Complexes for Electrocatalytic Proton Reduction DOI Creative Commons
Hang Cao,

Yuka Aoyama,

Kristen Mast

et al.

Published: May 8, 2024

Main-group metals as supporting ligands for transition offer potential bimetallic synergistic effects. We investigated a bismuth-palladium system utilizing PBiP pincer ligand (BiPdCl) precatalysts electrocatalytic proton reduction with thiophenol. Rinse tests revealed the formation of surface-bound active species, likely comprised Pd-based heterogenous materials. NMR and UV-visible spectroscopic studies unveiled that in diluted solutions polar coordinating solvents, chloride trans to bismuthane readily dissociates, affording solvent-coordinated species (BiPdsolvent) predominant solution species. Following thiol– solvent exchange, an equilibrium mixture solvent-bound thiolate complex (BiPdS) forms. The crystal structures BiPdS acetonitrile-coordinated model (BiPdAcN) shows thermodynamic influence ligand. Structural analysis, corroborated by computational investigations, suggests BiPdsolvent is primarily ligand-based than Pd-centered, hinting at Bi(III)–Pd(0) oxidation states rather Bi(I)–Pd(II) suggested Lewis structure BiPdsolvent. electron-rich Pd electron-poor Bi centers explain its electrochemical decomposition similar other Pd(0) Our findings shed light on electronic properties reactivities studied Bi–Pd compounds, offering example ambiguous within this system.

Language: Английский

Citations

1
Photocatalytic fluoroalkylation by ligand-to-metal charge transfer DOI Creative Commons
Jingyi Liu,

Zhenwei Cui,

Jingjing Bi

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: Sept. 6, 2024

Trifluoromethyl (CF

Language: Английский

Citations

0
Arylative difunctionalization of olefins using easily accessed organobismuth (V) reagents DOI
Nicholas D. Chiappini

Chem, Journal Year: 2024, Volume and Issue: 10(10), P. 2945 - 2947

Published: Oct. 1, 2024

Language: Английский

Citations

0
Transition-metal-free synthesis of arylboronates via thermal generation of aryl radicals from triarylbismuthines in air DOI Creative Commons
Yuki Yamamoto,

Yuki Konakazawa,

Kohsuke Fujiwara

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2577 - 2584

Published: Oct. 11, 2024

A simple and versatile synthesis of arylboronates has been achieved by using triarylbismuthines as aryl radical sources under transition-metal-free open-air conditions. Conventional methods required photoirradiation or electrolysis to generate radicals from triarylbismuthines. In this study, it was found that simply heating the solution in benzotrifluoride (BTF) air successfully led generation radicals, subsequent reaction with bis(pinacolato)diboron afforded a variety moderate good yields.

Language: Английский

Citations

0
Activation and C‒C Coupling of Aryl Iodides via Bismuth Photocatalysis DOI Creative Commons
Mauro Mato, Alexios Stamoulis, Paolo Cleto Bruzzese

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Abstract Within the emerging field of bismuth redox catalysis, catalytic formation C−C bonds using aryl halides would be highly desirable; yet such a process remains synthetic challenge. Herein, we present chemoselective bismuth‐photocatalyzed activation and subsequent coupling (hetero)aryl iodides with pyrrole derivatives to access C(sp 2 )−C(sp ) linkages through C−H functionalization. This unique reactivity is result complex featuring two state‐dependent interactions light, which 1) activates Bi(I) for oxidative addition via MLCT, 2) promotes homolytic cleavage Bi(III) intermediates LLCT process.

Language: Английский

Citations

0