Zinc and manganese redox potentials in organic solvents and their influence on nickel-catalyzed cross-electrophile coupling

Published: May 27, 2024

Zinc and manganese are widely used as reductants in synthetic methods, such nickel-catalyzed cross-electrophile coupling (XEC) reactions, but their redox potentials unknown organic solvents. Here, we show how open-circuit potential measurements may be to determine the thermodynamic of Zn Mn different solvents presence common reaction additives. The impact these is analyzed for a pair Ni-catalyzed each showing preference one two reductants. N-alkyl-2,4,6-triphenylpyridinium reagents (Katritzky salts) with aryl halides then compared under chemical conditions, using or reductants, electrochemical performed at applied corresponding reduction optimized achieve maximum yield. collective results illuminate important role reductant XEC reactions.

Language: Английский

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Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions

iScience, Journal Year: 2020, Volume and Issue: 23(8), P. 101419 - 101419

Published: July 30, 2020

Hydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role synthesis. However, the direct cleavage of Csp3-O bond alcohols with high selectivity efficiency, especially without assistance metal catalyst, has been a formidable challenge because strong dissociation energy unfavorable thermodynamics. Herein, efficient metal-free strategy that enables deoxygenation developed for first time, hydrazine reductant induced by light. This protocol features mild reaction conditions, excellent tolerance, abundant easily available starting materials, rendering selective variety 1° 2° alcohols, vicinal diols, β-1 even β-O-4 models natural wood lignin. also highlighted "traceless" non-toxic by-products N2 H2, readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being key intermediate this transformation.

Language: Английский

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Synergistic Relay Reactions To Achieve Redox‐Neutral α‐Alkylations of Olefinic Alcohols with Ruthenium(II) Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(11), P. 4544 - 4549

Published: Jan. 6, 2020

Herein, we report a ruthenium-catalyzed redox-neutral α-alkylation of unsaturated alcohols based on synergistic relay process involving olefin isomerization (chain walking) and umpolung hydrazone addition, which takes advantage the interaction between two rather inefficient individual reaction steps to enable an efficient overall process. This transformation shows compatibility hydrazone-type "carbanions" active protons in one-pot reaction, at same time achieves first Grignard-type nucleophilic addition using olefinic as latent carbonyl groups, providing higher yield corresponding secondary alcohol than classical aldehydes does. A broad scope hydrazones, including some complex structures, can be successfully employed this versatility approach its suitability alternative, means for generation tertiary alcohols.

Language: Английский

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Iron-Catalyzed Reductive Cross-Coupling of Heterocyclic Bromides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7700 - 7709

Published: April 24, 2025

Language: Английский

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Exploring the coordination confinement effect of divalent palladium/zero palladium doped polyaniline-networking: As an excellent-performance nanocomposite catalyst for C-C coupling reactions

Journal of Catalysis, Journal Year: 2020, Volume and Issue: 384, P. 177 - 188

Published: March 13, 2020

Language: Английский

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