Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 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.

Язык: Английский

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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

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

Язык: Английский

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Carbon Monoxide in Main-Group Chemistry

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(5), С. 2034 - 2050

Опубликована: Янв. 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.

Язык: Английский

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Forever young: the first seventy years of ferrocene

Dalton Transactions, Год журнала: 2022, Номер 51(21), С. 8085 - 8102

Опубликована: Янв. 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.

Язык: Английский

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Radical transformations for allene synthesis

Chemical Science, Год журнала: 2022, Номер 13(29), С. 8491 - 8506

Опубликована: Янв. 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

Язык: Английский

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Organic Photoredox-Catalyzed Silyl Radical Generation from Silylboronate

ACS Catalysis, Год журнала: 2022, Номер 12(13), С. 7804 - 7810

Опубликована: Июнь 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.

Язык: 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, Год журнала: 2022, Номер 13(11), С. 3169 - 3175

Опубликована: Янв. 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

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2023, Номер 52(9), С. 2946 - 2991

Опубликована: Янв. 1, 2023

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

Язык: Английский

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A light-driven enzymatic enantioselective radical acylation

Nature, Год журнала: 2023, Номер 625(7993), С. 74 - 78

Опубликована: Дек. 18, 2023

Язык: Английский

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

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 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.

Язык: Английский

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