Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

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Late-stage C–H functionalization offers new opportunities in drug discovery

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 522 - 545

Published: July 13, 2021

Language: Английский

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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: Toward Sustainability and Applications

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(2), P. 245 - 261

Published: Feb. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

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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Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 165 - 178

Published: March 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Language: Английский

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Proximity Electronic Effect of Ni/Co Diatomic Sites for Synergistic Promotion of Electrocatalytic Oxygen Reduction and Hydrogen Evolution

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 33(4)

Published: Nov. 13, 2022

Abstract The modulation effect manifests an encouraging potential to enhance the performance of single‐atom catalysts; however, in‐depth study about this for isolated diatomic sites (DASs) remains a great challenge. Herein, proximity electronic (PEE) Ni/Co DASs is proposed that anchored in N‐doped carbon (N‐C) substrate (NiCo DASs/N‐C) synergistic promoting electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution (HER). Benefiting from PEE adjacent Ni by four nitrogen (Ni‐N 4 ) moiety, NiCo DASs/N‐C catalyst exhibits superior ORR HER activity. In situ characterization results suggest Co (Co‐N as main active site O 2 adsorption‐activation process, which promotes formation key *OOH desorption *OH intermediate accelerate multielectron kinetics. Theoretical calculation reveals Ni‐N modulator can effectively adjust localization Co‐N site, *H adsorption on thereby boosting process significantly. This opens new opportunity rationally regulating catalytic centers well provides guidance designing high‐efficiency bifunctional electrocatalysts promising applications.

Language: Английский

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Interfacing single-atom catalysis with continuous-flow organic electrosynthesis

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(10), P. 3898 - 3925

Published: Jan. 1, 2022

This manuscript reviews for the first time developments at interface between organic electrosynthesis and single-atom catalysis, highlighting advantages in shifting from a batch to flow production.

Language: Английский

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Cu-Electrocatalytic Diazidation of Alkenes at ppm Catalyst Loading

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(27), P. 11980 - 11985

Published: June 30, 2022

The 1,2-diamine motif is prevalent in natural products, small-molecule pharmaceuticals, and catalysts for asymmetric synthesis. Transition metal catalyzed alkene diazidation has evolved to be an attractive strategy access vicinal primary diamines but remains challenging, especially practical applications, due the restriction a certain type of olefins, frequent use chemical oxidants, requirement high loadings (1 mol % or above). Herein we report scalable Cu-electrocatalytic reaction with 0.02 (200 ppm) copper(II) acetylacetonate as precatalyst without exogenous ligands. In addition its low catalyst loading, electrocatalytic method scalable, compatible broad range functional groups, applicable α,β-unsaturated carbonyl compounds mono-, di-, tri-, tetrasubstituted unactivated alkenes.

Language: Английский

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Organoelectrocatalysis Enables Direct Cyclopropanation of Methylene Compounds

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2343 - 2350

Published: Feb. 1, 2022

Cyclopropane is a prevalent structural unit in natural products and bioactive compounds. While the transition metal-catalyzed alkene cyclopropanation of functionalized compounds such as α-diazocarbonyl derivatives has been well established provides straightforward access to cyclopropanes, directly from more stable simpler methylene remained an unsolved challenge despite highly desirable benefits minimal prefunctionalization increased operational safety. Herein we report electrocatalytic strategy for active compounds, employing organic catalyst. The method shows broad substrate scope excellent scalability, requires no metal catalyst or external chemical oxidant, convenient several types cyclopropane-fused heterocyclic carbocyclic Mechanistic investigations suggest that reactions proceed through radical-polar crossover process form two new carbon-carbon bonds nascent cyclopropane ring.

Language: Английский

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