Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

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Synthesis and Transformations of NH‐Sulfoximines

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(69), P. 17293 - 17321

Published: Sept. 14, 2021

Recent years have seen a marked increase in the occurrence of sulfoximines chemical sciences, often presented as valuable motifs for medicinal chemistry. This has been prompted by both pioneering works taking sulfoximine containing compounds into clinical trials and concurrent development powerful synthetic methods. review covers recent developments synthesis concentrating on since 2015. includes extensive S-N S-C bond formations. Flow chemistry processes are also covered. Finally, subsequent transformations sulfoximines, particularly N-functionalization reviewed, including N-S, N-P, N-C forming cyclization reactions.

Language: Английский

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Facile and general electrochemical deuteration of unactivated alkyl halides

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 30, 2022

Abstract Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides OMs) using D 2 O as the economical deuterium source was reported. In addition to primary secondary halides, sterically hindered tertiary chlorides also work very well, affording target deuterodehalogenated products with excellent efficiency incorporation. More than 60 examples are provided, including late-stage dehalogenative natural products, pharmaceuticals, their derivatives, all incorporation (up 99% D), demonstrating potential utility developed method in organic synthesis. Furthermore, does not require external catalysts tolerates high current, showing possible use industrial applications.

Language: Английский

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Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: June 7, 2022

Over the past two decades, electro-organic synthesis has gained significant interest, both in technical and academic research as well terms of applications. The omission stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions organic chemistry. Even if it is well-known that every electrochemical oxidation only viable with an associated reduction reaction vice versa, relevance counter often less addressed. In this Review, importance corresponding highlighted how can affect performance selectivity electrolytic conversion. A selection common strategies unique concepts to tackle issue are surveyed provide guide select appropriate synthesis.

Language: Английский

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Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

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Nickel-mediated aerobic C(sp2)–nucleophile coupling reactions for late-stage diversification of aryl electrophiles

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Language: Английский

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Transition metal-catalyzed organic reactions in undivided electrochemical cells

Chemical Science, Journal Year: 2021, Volume and Issue: 12(39), P. 12866 - 12873

Published: Jan. 1, 2021

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts alter selectivity given transformation.

Language: Английский

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Redox-Neutral Cross-Coupling Amination with Weak N-Nucleophiles: Arylation of Anilines, Sulfonamides, Sulfoximines, Carbamates, and Imines via Nickelaelectrocatalysis

JACS Au, Journal Year: 2021, Volume and Issue: 1(7), P. 1057 - 1065

Published: June 15, 2021

A nickel-catalyzed cross-coupling amination with weak nitrogen nucleophiles is described. Aryl halides as well aryl tosylates can be efficiently coupled a series of N-nucleophiles, including anilines, sulfonamides, sulfoximines, carbamates, and imines via concerted paired electrolysis. Notably, electron-deficient anilines sulfonamides are also suitable substrates. Interestingly, when benzophenone imine applied in the arylation, product selectivity toward formation amine addressed by base switch. In addition, alternating current mode successfully applied. DFT calculations support facilitated reductive elimination pathway.

Language: Английский

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Decarboxylative sulfoximination of benzoic acids enabled by photoinduced ligand-to-copper charge transfer

Chemical Science, Journal Year: 2022, Volume and Issue: 13(45), P. 13611 - 13616

Published: Jan. 1, 2022

Sulfoximines are synthetically important scaffolds and serve roles in drug discovery. Currently, there is no solution to decarboxylative sulfoximination of benzoic acids; although thoroughly investigated, limited substrate scope harsh reaction conditions still hold back traditional thermal aromatic functionalization. Herein, we realize the first acids via photo-induced ligand copper charge transfer (copper-LMCT)-enabled carbometalation. The transformation proceeds under mild conditions, has a broad scope, can be applied late-stage functionalization complex small molecules.

Language: Английский

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Electrochemical NiH‐Catalyzed C(sp³)−C(sp³) Coupling of Alkyl Halides and Alkyl Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkenes for the construction Csp3 -Csp3 bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late-stage modification natural products drug derivatives. Mechanistic insights offer evidence process. sp3 -carbon-halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

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