Electrochemically Driven Nickel‐Catalyzed Halogenation of Unsaturated Halide and Triflate Derivatives DOI

Ming‐Yu Chen,

Sylvain Charvet, Pierre‐Adrien Payard

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(2)

Published: Nov. 6, 2023

Abstract A robust electrochemically driven nickel‐catalyzed halogen exchange of unsaturated halides and triflates (Br to Cl, I Br, OTf Cl) is reported. combination NiCl 2 ⋅ glyme as the precatalyst, 2,2′‐bipyridine a ligand, NMP solvent, electrochemistry allowed generation nickel species that promotes reductive elimination desired product. This paired electrochemical halogenation compatible with range triflates, including heterocycles, dihaloarenes, alkenes good functional‐group tolerance. Joint experimental theoretical mechanistic investigations highlighted three catalytic events: i) oxidative addition aryl halide Ni(0) deliver Ni(II) intermediate; ii) metathesis at Ni(II); iii) oxidation Ni(III) enable formation upon elimination. methodology allows replacement heavy halogens (I or Br) polar atoms (O) corresponding lighter more lipophilic Cl group block undesired reactivity modify properties drug agrochemical candidates.

Language: Английский

Phenalenyl-Based Photocatalyst for Bioinspired Oxidative Dehydrogenation of N-Heterocycles and Benzyl Alcohols DOI
Vishali Pathania, Sudipta Raha Roy

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4145 - 4155

Published: Feb. 28, 2024

The environmental benefits of molecular oxygen as the oxidizing agent in oxidation reactions that synthesize fine chemicals cannot be overstated. Increased interest developing robust photocatalysts is stimulated by fact current photocatalytic transformation boom has made previously inaccessible synthetic approaches possible. Motivated enzymatic catalysis, employing a reusable phenalenyl-based photocatalyst, we have successfully developed oxidative dehydrogenation utilizing greener oxidant. Under photoinduced conditions, different types saturated N-heterocycles and alcohols were dehydrogenated. versatility this bioinspired protocol demonstrated wide variety N-heteroaromatics, such quinoline, carbazole, quinoxaline, acridine, indole derivatives, well aldehydes ketones, synthesized. Detailed mechanistic studies validate proposed mechanism. Fluorescence lifetime CV experiments revealed crucial role water on efficiency reaction. present also provides chemoselectivity scalability, leading to superior results allowing for functionalization bioactive molecules at late stage sustainable manner.

Language: Английский

Citations

2
Inhibit effect of Pr，Ce，La or Yb doping on microwave-assisted pyrolysis of waste plastics for by-production oil over Co-Fe catalysts DOI
Bin Zhang, Yanan Li, Shuai Lu

et al.

Journal of Analytical and Applied Pyrolysis, Journal Year: 2024, Volume and Issue: 179, P. 106485 - 106485

Published: March 28, 2024

Language: Английский

Citations

2
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

2
Electrochemically Driven Nickel‐Catalyzed Halogenation of Unsaturated Halide and Triflate Derivatives DOI

Ming‐Yu Chen,

Sylvain Charvet, Pierre‐Adrien Payard

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 6, 2023

A robust electrochemically driven nickel-catalyzed halogen exchange of unsaturated halides and triflates (Br to Cl, I Br, OTf Cl) is reported. combination NiCl

Language: Английский

Citations

4
Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds DOI Creative Commons
Francesco Calogero,

Leonie Wilczek,

Emanuele Pinosa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 30, 2024

Abstract Excited states of radical anions derived from the photoreduction stable organic molecules are suggested to serve as potent reductants. However, excited these species too short‐lived allow bimolecular quenching processes. Recently, singlet state Meisenheimer complexes, which possess a long‐lived state, was identified competent for reduction challenging substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably and simply accessible different addition n BuLi readily available aromatic heterocycles investigated, photoreactivity generated studied. In this paper, we present straightforward preparation family powerful photoreductants (*E ox < −3 SCE in their states, determined by DFT time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation electron‐rich aryl chlorides form C−C bond through cyclization. Photophysical analyses computational studies combination with experimental mechanistic investigations demonstrate ability adduct act strong electron donor under visible light irradiation.

Language: Английский

Citations

0
Electrochemically Driven Nickel‐Catalyzed Halogenation of Unsaturated Halide and Triflate Derivatives DOI

Ming‐Yu Chen,

Sylvain Charvet, Pierre‐Adrien Payard

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(2)

Published: Nov. 6, 2023

Abstract A robust electrochemically driven nickel‐catalyzed halogen exchange of unsaturated halides and triflates (Br to Cl, I Br, OTf Cl) is reported. combination NiCl 2 ⋅ glyme as the precatalyst, 2,2′‐bipyridine a ligand, NMP solvent, electrochemistry allowed generation nickel species that promotes reductive elimination desired product. This paired electrochemical halogenation compatible with range triflates, including heterocycles, dihaloarenes, alkenes good functional‐group tolerance. Joint experimental theoretical mechanistic investigations highlighted three catalytic events: i) oxidative addition aryl halide Ni(0) deliver Ni(II) intermediate; ii) metathesis at Ni(II); iii) oxidation Ni(III) enable formation upon elimination. methodology allows replacement heavy halogens (I or Br) polar atoms (O) corresponding lighter more lipophilic Cl group block undesired reactivity modify properties drug agrochemical candidates.

Language: Английский

Citations

1