Metalla-electrocatalyzed C–H Activation by Earth-Abundant 3d Metals and Beyond

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(1), P. 84 - 104

Published: Dec. 19, 2019

To improve the efficacy of molecular syntheses, researchers wish to capitalize upon selective modification otherwise inert C-H bonds. The past two decades have witnessed considerable advances in coordination chemistry that set stage for transformative tools functionalizations. Particularly, oxidative C-H/C-H and C-H/Het-H transformations gained major attention because they avoid all elements substrate prefunctionalization. Despite advances, activations been dominated by precious transition metal catalysts based on palladium, ruthenium, iridium, rhodium, thus compromising sustainable nature overall activation approach. same holds true predominant use stoichiometric chemical oxidants regeneration active catalyst, prominently featuring hypervalent iodine(III), copper(II), silver(I) oxidants. Thereby, quantities undesired byproducts are generated, which preventive applications scale. In contrast, elegant merger homogeneous metal-catalyzed with electrosynthesis bears unique power achieve outstanding levels oxidant resource economy. Thus, contrast classical electrosyntheses control, metalla-electrocatalysis huge largely untapped potential unmet site selectivities means catalyst control. While indirect electrolysis using palladium complexes has realized, less toxic expensive base feature distinct beneficial assets toward this Account, I summarize emergence electrocatalyzed earth-abundant 3d metals beyond, a topical focus contributions from our laboratories through November 2019. cobalt electrocatalysis was identified as particularly powerful platform wealth transformations, including oxygenations nitrogenations well alkynes, alkenes, allenes, isocyanides, carbon monoxide, among others. As complementary tools, nickel, copper, very recently iron devised metalla-electrocatalyzed activations. Key success were detailed mechanistic insights, oxidation-induced reductive elimination scenarios. Likewise, development methods make weak O-coordination benefited crucial insights into catalyst's modes action experiment, operando spectroscopy, computation. Overall, thereby syntheses These electrooxidative frequently characterized improved chemoselectivities. Hence, ability dial redox at minimum level required desired transformation renders an ideal functionalization structurally complex molecules sensitive functional groups. This strategy was, inter alia, successfully applied scale-up continuous flow step-economical assembly polycyclic aromatic hydrocarbons.

Language: Английский

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Graphitic carbon nitride-based photocatalysts: Toward efficient organic transformation for value-added chemicals production

Molecular Catalysis, Journal Year: 2020, Volume and Issue: 488, P. 110902 - 110902

Published: April 11, 2020

Language: Английский

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Triplet Energy Transfer Photocatalysis: Unlocking the Next Level

Chem, Journal Year: 2020, Volume and Issue: 6(8), P. 1888 - 1903

Published: Aug. 1, 2020

Language: Английский

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Inside‐and‐Out Semiconductor Engineering for CO₂ Photoreduction: From Recent Advances to New Trends

Small Structures, Journal Year: 2020, Volume and Issue: 2(1)

Published: Sept. 30, 2020

Photocatalytic CO 2 reduction attracts substantial interests for the production of chemical fuels via solar energy conversion, but activity, stability, and selectivity products were severely determined by efficiencies light harvesting, charge migration, surface reactions. Structural engineering is a promising tactic to address aforementioned crucial factors boosting photoreduction. Herein, timely comprehensive review focusing on recent advances in photocatalytic conversion based design strategies over nano‐/microstructure, crystalline band structure, structure interface provided, which covers both thermodynamic kinetic challenges photoreduction process. The key parameters essential tailoring size, morphology, porosity, bandgap, surface, or interfacial properties photocatalysts are emphasized toward efficient selective into valuable chemicals. New trends structural meet demands prominent activity also introduced. It expected furnish guideline inside‐and‐out state‐of‐the‐art with well‐defined structures conversion.

Language: Английский

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

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(8), P. 1317 - 1340

Published: July 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.

Language: Английский

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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

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Recent advances in visible light-activated radical coupling reactions triggered by (i) ruthenium, (ii) iridium and (iii) organic photoredox agents

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(17), P. 9540 - 9685

Published: Jan. 1, 2021

Visible light-activated reactions continue to expand and diversify. The example shown here is a Birch reduction achieved by organophotoredox reagents.

Language: Английский

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Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

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Photophysics and photochemistry with Earth-abundant metals – fundamentals and concepts

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(4), P. 1057 - 1070

Published: Jan. 1, 2020

Recent exciting developments in the area of mononuclear photoactive complexes with Earth-abundant metal ions (Cu, Zr, Fe, Cr) for potential eco-friendly applications (phosphorescent) organic light emitting diodes, imaging and sensing systems, dye-sensitized solar cells as photocatalysts are presented. Challenges, particular extension excited state lifetimes, recent conceptual breakthroughs substituting precious rare-Earth (e.g. Ru, Ir, Pt, Au, Eu) these by abundant outlined selected examples. Relevant fundamentals photophysics photochemistry discussed first, followed instructive case studies.

Language: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

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