Unlocking the Potential of Deep Eutectic Solvents and Ligand‐to‐Metal Charge Transfer Processes: A Reusable Iron‐and‐UV‐Based System for Sustainable C‐C Bond Formation DOI Creative Commons
Nerea González‐Gallardo,

Alejandro Cores,

Xavier Marset

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 3, 2024

Abstract Catalytic C−H functionalization has provided new opportunities to access novel organic molecules more sustainably and efficiently. However, these procedures typically rely on precious metals or complex catalysts as well hazardous solvents reaction conditions. Herein, a pioneering methodology for direct C−C bond formation enabled by Ligand‐to‐Metal Charge Transfer (LMCT) mediated UV irradiation been developed using Deep Eutectic Solvents (DESs) sustainable media. This via radical addition electrophiles was successfully confirmed over broad scope of substrates. More importantly, this is the first example photocatalytic in DESs. An inexpensive abundant iron catalyst (FeCl 3 ) used under air mild Different functional groups were tolerated obtaining promising results that comparable those reported literature. Additionally, medium along with could be reused up 5 consecutive cycles without significant loss outcome. Several green metrics calculated compared conventional procedures, revealing advantages

Language: Английский

Iron‐Catalyzed, Light‐Driven Decarboxylative Alkoxyamination DOI Creative Commons

Milan Innocent,

Clément Tanguy,

Sigrid Gavelle

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(41)

Published: May 13, 2024

An iron-catalyzed visible-light driven decarboxylative alkoxyamination is disclosed. In the presence of FeBr

Language: Английский

Citations

3
Direct excitation of carbonyl cyclopropanes: From divergent pho-to-isomerization and annulation to unified reductive C-C cleavage DOI Creative Commons
Tin V. T. Nguyen, André Bossonnet, Duncan K. Brownsey

et al.

Published: May 21, 2024

We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon-carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process bicyclic products. Based these results, unified reductive ring-opening reaction was developed by using diphenyl disulfide as HAT reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH2 insertion into ,- bond both acyclic and cyclic un-saturated compounds. Our protocol therefore provides further tool for framework-editing carbocycles, com-plementing recent progress "skeletal editing" strategies.

Language: Английский

Citations

1
Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy DOI Creative Commons
Tin V. T. Nguyen, Duncan K. Brownsey, André Bossonnet

et al.

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

Published: Oct. 31, 2024

We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon-carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process bicyclic products. Based these results, unified reductive ring-opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH

Language: Английский

Citations

1
Direct excitation of carbonyl cyclopropanes: From divergent photo-isomerization and annulation to unified reductive C-C cleavage DOI Creative Commons
Tin V. T. Nguyen, André Bossonnet, Duncan K. Brownsey

et al.

Published: May 22, 2024

We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon-carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process bicyclic products. Based these results, unified reductive ring-opening reaction was developed by using diphenyl disulfide as HAT reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH2 insertion into alpha,beta- bond both acyclic and cyclic unsaturated compounds. Our protocol therefore provides further tool for framework-editing carbocycles, complementing recent progress "skeletal editing" strategies.

Language: Английский

Citations

1
Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy DOI
Tin V. T. Nguyen, Duncan K. Brownsey, André Bossonnet

et al.

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

Published: Oct. 31, 2024

Abstract We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon‐carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo‐Nazarov process bicyclic products. Based these results, unified reductive ring‐opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH 2 insertion into α,β bond both acyclic and cyclic unsaturated compounds. Our protocol provides further tool for modification carbon framework organic compounds, complementing recent progress “skeletal editing”.

Language: Английский

Citations

0
Unlocking the Potential of Deep Eutectic Solvents and Ligand‐to‐Metal Charge Transfer Processes: A Reusable Iron‐and‐UV‐Based System for Sustainable C‐C Bond Formation DOI Creative Commons
Nerea González‐Gallardo,

Alejandro Cores,

Xavier Marset

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 3, 2024

Abstract Catalytic C−H functionalization has provided new opportunities to access novel organic molecules more sustainably and efficiently. However, these procedures typically rely on precious metals or complex catalysts as well hazardous solvents reaction conditions. Herein, a pioneering methodology for direct C−C bond formation enabled by Ligand‐to‐Metal Charge Transfer (LMCT) mediated UV irradiation been developed using Deep Eutectic Solvents (DESs) sustainable media. This via radical addition electrophiles was successfully confirmed over broad scope of substrates. More importantly, this is the first example photocatalytic in DESs. An inexpensive abundant iron catalyst (FeCl 3 ) used under air mild Different functional groups were tolerated obtaining promising results that comparable those reported literature. Additionally, medium along with could be reused up 5 consecutive cycles without significant loss outcome. Several green metrics calculated compared conventional procedures, revealing advantages

Language: Английский

Citations

0