Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 415 - 431

Published: March 9, 2021

Efficient and selective molecular syntheses are paramount to

Language: Английский

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C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Enantioselective electrochemical cobalt-catalyzed aryl C–H activation reactions

Science, Journal Year: 2023, Volume and Issue: 379(6636), P. 1036 - 1042

Published: March 10, 2023

Enantioselective redox transformations typically rely on costly transition metals as catalysts and often stoichiometric amounts of chemical agents well. Electrocatalysis represents a more sustainable alternative, in particular through the use hydrogen evolution reaction (HER) place oxidant. In this work, we describe strategies for HER-coupled enantioselective aryl carbon-hydrogen bond (C-H) activation reactions using cobalt precious metal catalyst asymmetric oxidation. Thus, highly nitrogen-hydrogen (C-H N-H) annulations carboxylic amides were achieved, which gave access to point axially chiral compounds. Furthermore, cobalt-mediated electrocatalysis enabled preparation various phosphorus (P)-stereogenic compounds by selective desymmetrization dehydrogenative C-H reactions.

Language: Английский

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Base‐Promoted Electrochemical Co^II‐catalyzed Enantioselective C−H Oxygenation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 20, 2023

Metalla-electrocatalyzed C-H oxygenation represents one of the most straightforward and sustainable approaches to access valuable oxygenated molecules. Despite significant advances, development enantioselective electrochemical reaction is very challenging remains elusive. Herein, we described first CoII -catalyzed alkoxylation. A broad range enantioenriched alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up 98 % yield >99 ee). An unusual cobalt(III) alcohol complex was prepared fully characterized, which proven be a key intermediate this alkoxylation reaction. Mechanistic studies revealed that oxidation CoIII CoIV facilitated by base whole process proceeded through cobalt(III/IV/II) catalytic cycle.

Language: Английский

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Electrocatalytic Access to Azetidines via Intramolecular Allylic Hydroamination: Scrutinizing Key Oxidation Steps through Electrochemical Kinetic Analysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15360 - 15369

Published: July 10, 2023

Azetidines are prominent structural scaffolds in bioactive molecules, medicinal chemistry, and ligand design for transition metals. However, state-of-the-art methods cannot be applied to intramolecular hydroamination of allylic amine derivatives despite their underlying potential as one the most prevalent synthetic precursors azetidines. Herein, we report an electrocatalytic method sulfonamides access azetidines first time. The merger cobalt catalysis electricity enables regioselective generation key carbocationic intermediates, which could directly undergo C-N bond formation. mechanistic investigations including electrochemical kinetic analysis suggest that either catalyst regeneration by nucleophilic cyclization or second oxidation intermediate is involved rate-determining step (RDS) our protocol highlight ability electrochemistry providing ideal means mediate oxidation.

Language: Английский

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Renewable resources for sustainable metallaelectro-catalysed C–H activation

Chemical Science, Journal Year: 2020, Volume and Issue: 11(33), P. 8657 - 8670

Published: Jan. 1, 2020

The merger of C–H activation with electrosynthesis, powered by renewable energies and resources, will guide towards a sustainable future.

Language: Английский

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Insights into Cobalta(III/IV/II)‐Electrocatalysis: Oxidation‐Induced Reductive Elimination for Twofold C−H Activation

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(27), P. 10955 - 10960

Published: March 10, 2020

Abstract The merger of cobalt‐catalyzed C−H activation and electrosynthesis provides new avenues for resource‐economical molecular syntheses, unfortunately their reaction mechanisms remain poorly understood. Herein, we report the identification full characterization electrochemically generated high‐valent cobalt(III/IV) complexes as crucial intermediates in electrochemical oxygenations. Detailed mechanistic studies provided support an oxidatively‐induced reductive elimination via highly‐reactive cobalt(IV) intermediates. These key insights set stage unprecedented cobaltaelectro two‐fold C−H/C−H activation.

Language: Английский

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Electrooxidative Rhodium‐Catalyzed [5+2] Annulations via C−H/O−H Activations

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(12), P. 6419 - 6424

Published: Jan. 20, 2021

Abstract Electrooxidative annulations involving mild transition metal‐catalyzed C−H activation have emerged as a transformative strategy for the rapid construction of five‐ and six‐membered heterocycles. In contrast, we herein describe first electrochemical [5+2] cycloadditions to assemble valuable seven‐membered benzoxepine skeletons by C−H/O−H activation. The efficient alkyne annulation featured ample substrate scope, using electricity only oxidant. Mechanistic studies provided strong support rhodium(III/I) regime, benzoxepine‐coordinated rhodium(I) sandwich complex catalyst resting state, which was re‐oxidized rhodium(III) anodic oxidation.

Language: Английский

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Cobalt/Salox‐Catalyzed Enantioselective Dehydrogenative C−H Alkoxylation and Amination

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: Aug. 2, 2022

The past decade has witnessed a rapid progress in asymmetric C-H activation. However, the enantioselective alkoxylation and amination with alcohols free amines remains elusive. Herein, we disclose first dehydrogenative enabled by simple cobalt/salicyloxazoline (Salox) catalysis. use of cheap readily available cobalt(II) salts as catalysts Saloxs chiral ligands provides an efficient method to access P-stereogenic compounds excellent enantioselectivities (up >99 % ee). practicality this protocol is demonstrated gram-scale preparation further derivatizations resulting phosphinamides, which offering flexible alternative mono- diphosphine ligands. Preliminary mechanistic studies on reaction suggest that cobalt(III/IV/II) catalytic cycle might be involved.

Language: Английский

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Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

Advanced Science, Journal Year: 2022, Volume and Issue: 10(1)

Published: Nov. 18, 2022

Electro-organic synthesis has attracted a lot of attention in pharmaceutical science, medicinal chemistry, and future industrial applications energy storage conversion. To date, there not been detailed review on electro-organic with the strategy heterogeneous catalysis. In this review, most recent advances synthesizing value-added chemicals by catalysis are summarized. An overview electrocatalytic oxidation reduction processes as well paired electrocatalysis is provided, anodic alcohols (monohydric polyhydric), aldehydes, amines discussed. This also provides in-depth insight into cathodic carboxylates, carbon dioxide, CC, C≡C, reductive coupling reactions. Moreover, electro-synthesis methods, including parallel paired, sequential divergent convergent electrolysis, Additionally, strategies developed to achieve high electrosynthesis efficiency associated challenges addressed. It believed that promising direction organic electrochemistry, offering numerous opportunities develop new reaction methods.

Language: Английский

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