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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New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Год журнала: 2020, Номер 6(8), С. 1317 - 1340

Опубликована: Июль 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

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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Synthetic Photoelectrochemistry

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(29), С. 11732 - 11747

Опубликована: Дек. 5, 2019

Photoredox catalysis (PRC) and synthetic organic electrochemistry (SOE) are often considered competing technologies in synthesis. Their fusion has been largely overlooked. We review state-of-the-art photoelectrochemistry, grouping examples into three categories: 1) electrochemically mediated photoredox (e-PRC), 2) decoupled photoelectrochemistry (dPEC), 3) interfacial (iPEC). Such synergies prove beneficial not only for "greenness" chemical selectivity, but also the accumulation of energy accessing super-oxidizing or -reducing single electron transfer (SET) agents. Opportunities challenges this emerging exciting field discussed.

Язык: Английский

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Making electrochemistry easily accessible to the synthetic chemist

Green Chemistry, Год журнала: 2020, Номер 22(11), С. 3358 - 3375

Опубликована: Янв. 1, 2020

This tutorial bridges an important knowledge gap by providing easily accessible introduction that enables synthetic chemists to explore electrochemistry.

Язык: Английский

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Nitrogen-Centered Radicals in Functionalization of sp² Systems: Generation, Reactivity, and Applications in Synthesis

Chemical Reviews, Год журнала: 2022, Номер 122(9), С. 8181 - 8260

Опубликована: Март 14, 2022

The chemistry of nitrogen-centered radicals (NCRs) has plentiful applications in organic synthesis, and they continue to expand as our understanding these reactive species increases. utility intermediates is demonstrated the recent advances C–H amination (di)amination alkenes. Synthesis previously challenging structures can be achieved by efficient functionalization sp2 moieties without prefunctionalization, allowing for faster more streamlined synthesis. This Review addresses generation, reactivity, application NCRs, including, but not limited to, iminyl, aminyl, amidyl, aminium species. Contributions from early discovery up most examples have been highlighted, covering radical initiation, thermolysis, photolysis, and, recently, photoredox catalysis. Radical-mediated intermolecular (hetero)arenes occur with a variety complex amine precursors, generating aniline derivatives, an important class drug development. Functionalization olefins achievable high anti-Markovnikov regioselectivity allows access difunctionalized when intermediate carbon are trapped. Additionally, reactivity NCRs harnessed rapid construction N-heterocycles such pyrrolidines, phenanthridines, quinoxalines, quinazolinones.

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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Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2313 - 2382

Опубликована: Янв. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Язык: Английский

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Merging photochemistry with electrochemistry in organic synthesis

Organic Chemistry Frontiers, Год журнала: 2019, Номер 7(1), С. 131 - 135

Опубликована: Ноя. 1, 2019

Recent advances merging photochemistry with electrochemistry in organic synthesis are highlighted.

Язык: Английский

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Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(6), С. 1132 - 1142

Опубликована: Янв. 1, 2021

Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of visible photon (>4.0 V vs. SCE) in anti-Kasha photo(electro)chemical super-oxidations arenes.

Язык: Английский

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