An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons <i>via</i> photo-induced ligand to metal charge transfer

Hu, Ao-Men; Tu, Jia-Lin; Luo, Mengqi; Yang, Chao; Guo, Lin; Xia, Wujiong

doi:10.1039/d3qo01081c

Org. Chem. Front.

2023

DOI: 10.1039/d3qo01081c

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An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons via photo-induced ligand to metal charge transfer

Ao-Men Hu,

Jia-Lin Tu,

Mengqi Luo

et al.

Abstract: Sulfur-containing compounds are commonly present in both natural and synthetic bioactive molecules. The ability to construct C−S bond using inexpensive and easily accessible raw materials under mild conditions is an...

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2024

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Cited by 25 publications

References 81 publications

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Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Wu,

2024

Adv Synth Catal

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Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation of alkoxy radicals through chlorine radical‐induced alkoxy radical formation, followed by β‐scission and trapping of the resulting carbon radicals with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). This reaction exhibits a broad substrate scope (40 examples), including primary and secondary alcohols that are prone to oxidation by the combination of TEMPO and iron. Mechanistic investigations have revealed that enhanced coordination of the chloride ion with the iron center inhibits the OH oxidation process, thereby enabling the tolerance of primary and secondary alcohols.

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Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Wu,

2024

Adv Synth Catal

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Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Tu,

Shen,

Huang

2024

Adv Synth Catal

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Aryl radicals are important intermediates in organic synthesis. The generation of these reactive species via direct decarboxylation of inexpensive and readily available aromatic carboxylic acids is an attractive goal. However, such a process intrinsically exhibits high energy barriers to overcome, which in consequence usually require precious metal catalysis, stoichiometric oxidants and harsh conditions, suffering from limitations such as poor functional group tolerance and low atom economy. In recent years, visible‐light‐induced photochemical reactions have provided new approaches to address this challenge. Three major strategies have been introduced in this emerging field: 1) one‐pot in‐situ activation of benzoic acids to generate intermediates such as benzoyl hypobromites or hypoiodites; 2) the use of specialized photocatalysts like biphenyl/1,4‐dicyanobenzene to promote decarboxylation through photo‐induced electron transfer or charge transfer processes; 3) photo‐induced LMCT (Ligand‐to‐Metal Charge Transfer) strategy where copper or iron salts coordinate to the carboxylate anion and generate aromatic radicals upon visible light excitation. On the basis of these three strategies, this review will systematically summarize the development of visible‐light‐induced direct decarboxylative functionalization of aromatic carboxylic acids, focusing on the reaction mechanism and substrate scope, and discuss their prospects in organic synthesis.

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Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Wu,

Chen,

Liu

et al. 2024

Angewandte Chemie

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A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination of this deacylative process with SN2 or coupling reactions provides novel and convenient modular strategies toward unsymmetrical or symmetric disulfides. Reactivity studies favor a bromine radical that initiates a HAT (Hydrogen Atom Transfer) from the aminal intermediate resulting in expulsion of a C‐centered radical that is intercepted to make C–S and C–Se bonds. Gram scale reactions, broad substrate scope and tolerance towards various functional groups render this method appealing for future applications in the synthesis of organosulfur and selenium complexes.

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An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons via photo-induced ligand to metal charge transfer

Abstract: Sulfur-containing compounds are commonly present in both natural and synthetic bioactive molecules. The ability to construct C−S bond using inexpensive and easily accessible raw materials under mild conditions is an...

Cited by 25 publications

References 81 publications

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

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