Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency

Language: Английский

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Palladium-catalyzed selective alkoxycarbonylation of different alcohols toward the direct synthesis of cyclobutanecarboxylates

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115956 - 115956

Published: Jan. 1, 2025

Language: Английский

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Photo-Promoted carbonylative Difunctionalization of alkenes toward β-Aminoketones

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115935 - 115935

Published: Jan. 1, 2025

Language: Английский

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Recent advances in light-induced carbonylation utilizing carbon monoxide as a carbonyl source: Applications and prospective developments

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 574, P. 114859 - 114859

Published: Jan. 23, 2025

Language: Английский

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Single-Electron-Transfer-Mediated Carbonylation Reactions

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

ConspectusTransition-metal-catalyzed carbonylation coupling methods have been accepted as an essential tool for producing carbonylated products over the past few decades. Despite its long-standing history and widespread industrial applications, several challenges remain in chemistry. These include reliance on precious metal catalysts, need of high-energy radiation, difficulties unactivated chemical bonds, etc. As alternative to classic two-electron transfer process, single-electron-transfer (SET)-mediated has emerged a powerful achieve elusive transformations. Over years, commonly available functional handles, such alkenes alkyl halides, via single-electron pathway valuable area research.Our team dedicated developing new reactions using bulk chemicals construct high-value products. broad synthetic motivating us explore SET-mediated transformations two key classes chemicals: alkanes halides. Specifically, our work centered main approaches: (1) Single-electron reduction C(sp3)-X bonds: this strategy leverages activate promoting formation carbon radicals, which turn promotes subsequent addition metals or CO. However, significant challenge lies highly negative potential certain substrates [Ered < -2 V compared saturated calomel electrode (SCE) iodides]. these challenges, intrinsic reducibility CO reactivity various carbonyl-metal intermediates facilitate smooth reaction progress. (2) oxidative C(sp3)-H emphasizes efficiency, high atomic utilization, minimal waste by bypassing traditional preactivation methods. Using 3d we successfully performed aminocarbonylation alkoxycarbonylation wide range bonds (such those aliphatic alkanes, ethers, amines, etc.). The above approaches also enabled radical relay alkenes, allowing precise control pathways. Such improves both efficiency selectivity. advancements transition photoredox catalysis resulting oxyalkylative carbonylation, aminoalkylative fluoroalkylative double rearrangement carbonylation.SET-mediated significantly enhances sustainability scalability process reducing catalysts enabling milder conditions. Additionally, carefully controlling intermediates, fine-tuned produce with This flexibility expands applications chemistry processes. Finally, place particular emphasis application drug discovery, where they serve handles late-stage modification bioactive molecules. applicability enriches toolbox synthesis, efficient functionalization complex versatile approach accelerate discovery novel therapeutic agents, making it critical modern medicinal

Language: Английский

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Photo‐Promoted Nitrogen‐Centered Radical Mediated Intermolecular Aminative Carbonylation of Tertiary Allyl Alcohols to Access β‐Amino Ketones through (Hetero)Aryl Migration

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Carbon monoxide, as a crucial C1 synthon, has been widely used in the difunctionalization of alkenes. Additionally, nitrogen‐centered radicals (NCRs) are also effective intermediates for constructing C−N bonds. Herein, radical‐mediated aminative carbonylation strategy producing β ‐amino ketones from tertiary allyl alcohols disclosed. Good yields with different functional groups were generated effectively under light irradiation.

Language: Английский

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Carbonylative five-component synthesis of amides and esters with α-quaternary carbon center

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111150 - 111150

Published: March 1, 2025

Language: Английский

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Emerging trends in CO carbonylation

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102503 - 102503

Published: April 1, 2025

Language: Английский

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Functionalized Oxindole Construction via a Cyano Migration and Cyclization Relay Strategy

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

A visible-light-induced trifunctionalization of unactivated alkenes for building functionalized oxindoles through a radical cyano migration strategy is reported. This transformation employs tandem alkene sulfonylation-initiated migration/cyclization cascade process. features stable and easily accessible substrates, mild reaction conditions, metal-free catalysts, the capability late-stage functionalization.

Language: Английский

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Access to Spirocyclic Vinyl Sulfones via Radical Cyclization and Functional Group Migration

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Spirocyclic vinyl sulfones, which incorporate the three-dimensional structure inherent to spiro compounds and Michael acceptor reactivity associated with hold promise for novel biological activities. The lack of efficient synthetic methods, however, hinders their extensive investigations in drug discovery development. In this work, we describe a practical versatile approach synthesis multi-functionalized spirocyclic sulfones from easily available materials. reaction proceeds efficiently through cascade radical cyclization followed by (hetero)aryl migration. protocol features mild photocatalytic conditions provides access diverse range products, enabling construction complex scaffolds, including medium-sized ring-fused sulfones.

Language: Английский

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