Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2752 - 2906

Опубликована: Авг. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Язык: Английский

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

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 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.

Язык: Английский

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Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(29), С. 10882 - 10889

Опубликована: Июль 13, 2021

We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl coupling reactions abundant but difficult to reduce chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled key terminal reductant byproduct, carbon dioxide anion.

Язык: Английский

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Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(28), С. 12567 - 12583

Опубликована: Июль 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.

Язык: Английский

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Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(12)

Опубликована: Сен. 3, 2021

Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in much greener way broadens redox window possible transformations. Herein, most recent contributions are reviewed, demonstrating exciting opportunities, namely, combination with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy sensitization), scalability up to multigram scale, novel selectivities SET super-oxidations/reductions importance precomplexation temporally enable excited ion catalysis.

Язык: Английский

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Exploring Electrochemical C(sp³)–H Oxidation for the Late-Stage Methylation of Complex Molecules

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(3), С. 1187 - 1197

Опубликована: Янв. 11, 2022

The "magic methyl" effect, a dramatic boost in the potency of biologically active compounds from incorporation single methyl group, provides simple yet powerful strategy employed by medicinal chemists drug discovery process. Despite significant advances, methodologies that enable selective C(sp3)–H methylation structurally complex agents remain very limited. In this work, we disclose modular, efficient, and for α-methylation protected amines (i.e., amides, carbamates, sulfonamides) means electrochemical oxidation. Mechanistic analysis guided our development an improved protocol on basis classic Shono oxidation reaction, which features broad reaction scope, high functional group compatibility, operational simplicity. Importantly, system is amenable to late-stage functionalization targets containing basic nitrogen groups are prevalent medicinally agents. When combined with organozinc-mediated C–C bond formation, enabled direct myriad amine derivatives including those have previously been explored effect. This synthesis thus circumvents multistep de novo currently necessary access such has potential accelerate efforts.

Язык: Английский

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Overcoming Limitations in Decarboxylative Arylation via Ag–Ni Electrocatalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(38), С. 17709 - 17720

Опубликована: Сен. 15, 2022

A useful protocol for achieving decarboxylative cross-coupling (DCC) of redox-active esters (RAE, isolated or generated in situ) and halo(hetero)arenes is reported. This pragmatically focused study employs a unique Ag-Ni electrocatalytic platform to overcome numerous limitations that have plagued this strategically powerful transformation. In its optimized form, coupling partners can be combined surprisingly simple way: open the air, using technical-grade solvents, an inexpensive ligand Ni source, substoichiometric AgNO3, proceeding at room temperature with commercial potentiostat. Most importantly, all results are placed into context by benchmarking state-of-the-art methods. Applications presented simplify synthesis rapidly enable access challenging chemical space. Finally, adaptation multiple scale regimes, ranging from parallel milligram-based decagram recirculating flow presented.

Язык: Английский

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Interfacing single-atom catalysis with continuous-flow organic electrosynthesis

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 3898 - 3925

Опубликована: Янв. 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.

Язык: Английский

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A tutorial on asymmetric electrocatalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(23), С. 8106 - 8125

Опубликована: Янв. 1, 2023

This tutorial review delves into the unique advantages of electrochemistry in context asymmetric catalysis, first providing a brief introduction to electrosynthesis, then exploring representative case studies with mechanistic focus.

Язык: Английский

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Generality-oriented optimization of enantioselective aminoxyl radical catalysis

Science, Год журнала: 2023, Номер 380(6646), С. 706 - 712

Опубликована: Май 18, 2023

Catalytic enantioselective methods that are generally applicable to a broad range of substrates rare. We report strategy for the oxidative desymmetrization

Язык: Английский

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