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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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Language: Английский

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Carbon Monoxide in Main-Group Chemistry

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2034 - 2050

Published: Jan. 24, 2022

The usage of carbon monoxide (CO) as a C1 feedstock for carbonylation has been an important subject numerous studies over century. chemistry in this field evolved significantly, and several processes (e.g., Fischer-Tropsch, Monsanto, Cativa process) have even industrialized to serve humankind our daily lives. CO is also crucial ligand (carbonyl) organometallic chemistry, transition-metal carbonyl complexes widely used homogeneous catalysts various chemical transformations. Historically, carbonyls considered be dominant these purposes. In recent decades, main-group elements, especially naturally abundant elements the Earth's crust such silicon aluminum, gained much attention, they are eco-friendly low toxicity compared late transition metals. Recent developments revealed reactivity which can mimic that toward small molecules H2, alkenes, alkynes, along with monoxide. This Perspective highlights activation by compounds leads formation or insertion into element center well reductive homologation CO.

Language: Английский

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Forever young: the first seventy years of ferrocene

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(21), P. 8085 - 8102

Published: Jan. 1, 2022

The discovery of ferrocene seventy years ago has revolutionised chemical research and opened a way to its applications in diverse fields. These developments are succinctly presented this perspective.

Language: Английский

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Radical transformations for allene synthesis

Chemical Science, Journal Year: 2022, Volume and Issue: 13(29), P. 8491 - 8506

Published: Jan. 1, 2022

Allenes are valuable organic molecules that feature unique physical and chemical properties. They not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such pharmaceuticals, functional materials. Therefore, many remarkable elegant methodologies have been established synthesis allenes. Recently, more methods radical allenes developed, clearly emphasizing associated great synthetic values. In this perspective, we will discuss recent important advances

Language: Английский

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Organic Photoredox-Catalyzed Silyl Radical Generation from Silylboronate

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(13), P. 7804 - 7810

Published: June 16, 2022

A visible-light-driven silyl radical generation method from silylboronates has been developed. The activation of with a catalytic amount mild base promoted the single-electron oxidation process to form radicals. Facile single electron transfer for borate readily occurred without hydrogen atom hydrosilane in presence various photoredox catalysts. Combining this protocol radical-mediated N-heterocyclic carbene catalysis enabled acylsilylation alkenes via relay generation. Furthermore, recent advanced methods synthesis significantly improved utility process.

Language: Английский

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NHC and visible light-mediated photoredox co-catalyzed 1,4-sulfonylacylation of 1,3-enynes for tetrasubstituted allenyl ketones

Chemical Science, Journal Year: 2022, Volume and Issue: 13(11), P. 3169 - 3175

Published: Jan. 1, 2022

The modulation of selectivity highly reactive carbon radical cross-coupling for the construction C-C bonds represents a challenging task in organic chemistry. N-Heterocyclic carbene (NHC) catalyzed transformations have opened new avenue acyl With this method, selective an with alkyl efficient was successfully realized. However, reaction radicals vinyl has been much less investigated. We herein describe NHC and visible light-mediated photoredox co-catalyzed 1,4-sulfonylacylation 1,3-enynes, providing structurally diversified valuable tetrasubstituted allenyl ketones. Mechanistic studies indicated that ketyl are formed from aroyl fluorides via oxidative quenching photocatalyst excited state, generated chemo-specific sulfonyl addition to finally, key provides

Language: Английский

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N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 2946 - 2991

Published: Jan. 1, 2023

This review discusses the applications of N-heterocyclic carbene ligands and their influence on reactivity selectivity Ni-catalysed alkene functionalisations.

Language: Английский

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A light-driven enzymatic enantioselective radical acylation

Nature, Journal Year: 2023, Volume and Issue: 625(7993), P. 74 - 78

Published: Dec. 18, 2023

Language: Английский

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Carbene-stabilized enantiopure heterometallic clusters featuring EQE of 20.8% in circularly-polarized OLED

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 11, 2023

Bright and efficient chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials diodes. To date, highly organic diodes (CP-OLEDs) with enantiopure have not been reported. Herein, through rational design of a multidentate N-heterocyclic carbene (NHC) ligand modular building strategy, we synthesize series Au(I)-Cu(I) exceptional stability. Modulation the ligands stabilize excited states to allow thermally activated delayed fluorescence, resulting highest orange-red photoluminescence quantum yields over 93.0% solid state, which is accompanied by luminescence. Based on solution process, prototypical CP-OLED considerably high external efficiency 20.8% prepared. These results demonstrate extensive designability NHC polymetallic performance chiroptical applications.

Language: Английский

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