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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Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 684 - 692

Published: Feb. 2, 2025

Herein, we report a scalable and mild strategy for the monofluoroalkylation of wide array Giese acceptors via visible-light-mediated photoredox catalysis in continuous flow. The use flow technology significantly enhances productivity scalability, whereas mildness conditions functional group tolerance are ensured by leveraging 4CzIPN, transition-metal-free organic photocatalyst. Structurally diverse secondary tertiary monofluoroalkyl radicals can thus be accessed from readily available α-monofluorocarboxylic acids. Given reaction conditions, this protocol is also amenable to late-stage functionalization biologically relevant molecules such as menthol, amantadine, bepotastine, estrone derivatives, rendering it suitable application drug discovery programs, which introduction fluorinated fragments highly sought after. This method was extended enable reductive multicomponent radical-polar crossover transformation rapidly increase complexity assembled architectures single synthetic operation.

Language: Английский

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Iron–Cobalt Dual Catalysis for the Synthesis of Alkenyl Amino Acids and Modification of Peptides

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

Published: April 6, 2025

Herein, we report an Fe/Co dual-catalyzed strategy for synthesizing alkenyl unnatural amino acids and peptide modifications. This approach utilizes aspartic acid glutamic derivatives as alkyl radical precursors. It avoids the use of expensive photoredox catalysts substrate preactivation while preserving chirality acids. Furthermore, this enables both modification peptides synthesis amino-acid-based drug candidates boron-neutron capture therapy (BNCT).

Language: Английский

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Iron-Photocatalyzed Decarboxylative Alkylation of Carboxylic Acids with Morita–Baylis–Hillman Acetates

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 27, 2024

We present an iron-photocatalyzed decarboxylative alkylation strategy involving carboxylic acids and Morita–Baylis–Hillman (MBH) acetates to synthesize E-type tri- tetrasubstituted alkenes with moderate excellent stereoselectivity (E/Z ratio up >19:1). This method is applicable a broad range of structurally diverse primary, secondary, tertiary alkyl acids, as well complex pharmaceutical natural achieving efficient various MBH under mild conditions (>60 examples, yields 96%). approach offers powerful for streamlined alkylation.

Language: Английский

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