A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions DOI Creative Commons
Ann M. May, Jillian L. Dempsey

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6661 - 6678

Published: Jan. 1, 2024

Ligand-to-metal charge transfer (LMCT) excited states showcase promise in enabling photochemical reactions. This article details design principles to enable low energy LMCT and notable examples that drive reactions from these states.

Language: Английский

Iron-mediated modular decarboxylative cross-nucleophile coupling DOI Creative Commons
Grace A. Lutovsky, Samuel N. Gockel, Mark W. Bundesmann

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(6), P. 1610 - 1621

Published: May 4, 2023

Language: Английский

Citations

50
Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis** DOI Creative Commons
Sara Fernández‐García, Veronika O. Chantzakou, Francisco Juliá‐Hernández

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 13, 2023

Trifluoroacetates are the most abundant and accessible sources of trifluoromethyl groups, which key components in pharmaceuticals agrochemicals. The generation reactive radicals from trifluoroacetates requires their decarboxylation, is hampered by high oxidation potential. This constitutes a major challenge for redox-based methods, because need to pair redox potentials with trifluoroacetate. Here we report strategy based on iron photocatalysis promote direct photodecarboxylation that displays reactivity features escape limitations. Our synthetic design has enabled use trifluoromethylation more easily oxidizable organic substrates, offering new opportunities late-stage derivatization campaigns using chemical feedstocks, Earth-abundant catalysts, visible-light.

Language: Английский

Citations

49
Photochemical iron-catalyzed decarboxylative azidation via the merger of ligand-to-metal charge transfer and radical ligand transfer catalysis DOI Creative Commons

Shih‐Chieh Kao,

Kang‐Jie Bian,

Xiaowei Chen

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(6), P. 100603 - 100603

Published: April 12, 2023

Language: Английский

Citations

47
Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp3)−H Alkenylation** DOI

Long Zou,

Xiaofan Wang,

Siqi Xiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

Citations

46
A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions DOI Creative Commons
Ann M. May, Jillian L. Dempsey

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6661 - 6678

Published: Jan. 1, 2024

Ligand-to-metal charge transfer (LMCT) excited states showcase promise in enabling photochemical reactions. This article details design principles to enable low energy LMCT and notable examples that drive reactions from these states.

Language: Английский

Citations

46