Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

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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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Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12567 - 12583

Published: July 11, 2022

Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions that have received tremendous attention in recent years. In contrast, processes combine these modalities, an area termed electrophotocatalysis, until recently remained quite rare. However, over past several years a number reports this shown potential combining power light electrical energy to realize new catalytic transformations. Electrophotocatalysis offers ability perform photoredox without need large quantities stoichiometric or superstoichiometric oxidants reductants by making use electrochemical as electron source sink. addition, electrophotocatalysis is readily amenable generation open-shell photocatalysts, which tend exceptionally strong redox potentials. way, potent yet selective been realized under relatively mild conditions. This Perspective highlights advances provides some possible avenues future work growing area.

Language: Английский

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Direct decarboxylative Giese reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(4), P. 1415 - 1453

Published: Jan. 1, 2022

This review summarizes recent progress on using carboxylic acids directly as convenient precursors for the 1,4-radical conjugate addition (Giese) reaction.

Language: Английский

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Advancing mechanochemical synthesis by combining milling with different energy sources

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 7(1), P. 51 - 65

Published: Nov. 21, 2022

Language: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

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TEMPO-Enabled Electrochemical Enantioselective Oxidative Coupling of Secondary Acyclic Amines with Ketones

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(38), P. 15599 - 15605

Published: Sept. 17, 2021

An electrochemical asymmetric coupling of secondary acyclic amines with ketones via a Shono-type oxidation has been described, affording the corresponding amino acid derivatives good to excellent diastereoselectivity and enantioselectivity. The addition an N-oxyl radical as redox mediator could selectively oxidize substrate rather than product, although their potential difference is subtle (about 13 mV). This transformation proceeds in absence stoichiometric additives, including metals, oxidants, electrolytes, which gives it functional group compatibility. Mechanistic studies suggest that proton-mediated racemization product prevented by reduction protons at cathode.

Language: Английский

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Nickel-Catalyzed Enantioselective Electrochemical Reductive Cross-Coupling of Aryl Aziridines with Alkenyl Bromides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6270 - 6279

Published: March 7, 2023

An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides has been developed, affording enantioenriched β-aryl homoallylic amines excellent E-selectivity. This electroreductive strategy proceeds in the absence heterogeneous metal reductants and sacrificial anodes by employing constant current electrolysis an undivided cell triethylamine as a terminal reductant. The reaction features mild conditions, remarkable stereocontrol, broad substrate scope, functional group compatibility, which was illustrated late-stage functionalization bioactive molecules. Mechanistic studies indicate that this transformation conforms stereoconvergent mechanism aziridine is activated through nucleophilic halide ring-opening process.

Language: Английский

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Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 26, 2022

Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.

Language: Английский

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Electrocarboxylation of Aryl Epoxides with CO₂for the Facile and Selective Synthesis of β‐Hydroxy Acids

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

Published: July 30, 2022

Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.

Language: Английский

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