Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: April 30, 2024

Abstract An electrochemical radical Truce Smiles rearrangement of N‐allylbenzamides is documented herein. The selective 1,4‐aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β‐arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N‐allylbenzamide crucial outcompete undesired 6‐ endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Formate Salts: The Rediscovery of Their Radical Reaction under Light Irradiation Opens New Avenues in Organic Synthesis DOI

Qing Shen,

Kun Cao,

Xiaoqing Wen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4274 - 4293

Published: Aug. 17, 2024

Abstract Formates are abundantly available and inexpensive commodity chemical, widely used in laboratory industrial organic synthesis. promising hydrogen carrier green C1 source, have also been a subject of research as SET reductants recent years. Compared to the toxic flammable gas carbon monoxide, which serves formates easier handle, store, transport, more environmentally friendly. Therefore, studies radical reactions, formate is not only an ideal source carbonyl, great significance synthesize carboxyl compounds with various structures, but reductant for editing molecules either scientific or production. The activation conversion formate, reductant, very challenging hot field

Language: Английский

Citations

4
Photo-catalyst-free photomediated pinacol coupling of ketones/aldehydes by formate at room temperature DOI

Qing Shen,

Kun Cao, Xueqin Chen

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(23), P. 9665 - 9671

Published: Jan. 1, 2023

In this work, a highly effective metal-free and photo-catalyst-free method for the reductive coupling of carbonyl compounds to produce pinacols using formate under photoirradiation has been reported.

Language: Английский

Citations

11
Recent developments for the synthesis of the dihydroisoquinolin-1(2H)-ones via cyclization of N-allylbenzamides DOI
Yan‐Ning Niu, Keyu Wang, Fuzhong Han

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134497 - 134497

Published: Jan. 1, 2025

Language: Английский

Citations

0
Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 30, 2024

An electrochemical radical Truce Smiles rearrangement of N-allylbenzamides is documented herein. The selective 1,4-aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β-arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N-allylbenzamide crucial outcompete undesired 6-endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Citations

3
Metal-free synthesis of 5-alkylated dihydrobenzimidazo[2,1-a]isoquinolines from pendent unactivated alkenes via double C–H functionalizations DOI
Mai Zhang,

Xiao-Jing Tian,

Yihan Gao

et al.

Tetrahedron, Journal Year: 2023, Volume and Issue: 141, P. 133510 - 133510

Published: June 10, 2023

Language: Английский

Citations

5
Metal‐Catalyzed, Photo‐Assisted Selective Transformation of Tertiary Alkylbenzenes and Polystyrenes into Carbonyl Compounds DOI
Garazi Urgoitia, María Teresa Herrero, Raúl SanMartı́n

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(17)

Published: June 17, 2022

Abstract Every year, thousands of tons polystyrene are produced and discarded, filling landfills polluting the marine environment. Although several degradation alternatives have been proposed, need for an effective procedure chemical recycling still remains. Here, a vanadium‐catalyzed reaction, assisted by visible light, promoted direct, selective conversion tertiary alkylbenzenes into acetophenone other ketone derivatives. Likewise, standard samples as well polystyrenes from insulation packaging waste could be chemically recycled in scalable way regardless their molecular weight, polydispersity, or form. Preliminary mechanistic investigations revealed participation singlet oxygen, superoxide, hydroxyl radical species this homogenously catalyzed process. Acetophenone used additive to accelerate reaction increase yields some cases.

Language: Английский

Citations

5
Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: April 30, 2024

Abstract An electrochemical radical Truce Smiles rearrangement of N‐allylbenzamides is documented herein. The selective 1,4‐aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β‐arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N‐allylbenzamide crucial outcompete undesired 6‐ endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Citations

0