Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1925 - 2016

Опубликована: Сен. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Язык: Английский

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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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Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis

Chem Catalysis, Год журнала: 2021, Номер 1(3), С. 523 - 598

Опубликована: Май 24, 2021

Язык: Английский

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Visible light promoted cross-dehydrogenative coupling: a decade update

Green Chemistry, Год журнала: 2020, Номер 22(20), С. 6632 - 6681

Опубликована: Янв. 1, 2020

In this review, all the visible light promoted cross-dehydrogenative coupling methodologies that have been developed over last decade are disclosed.

Язык: Английский

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Cross-dehydrogenative coupling: a sustainable reaction for C–C bond formations

Green Chemistry, Год журнала: 2021, Номер 23(18), С. 6789 - 6862

Опубликована: Янв. 1, 2021

We provide a review of the progress cross-dehydrogenative coupling reactions in constructing wide variety C–C bonds. Sustainable can be combined with multiple forms energy output.

Язык: Английский

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Benzylic C−H acylation by cooperative NHC and photoredox catalysis

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Апрель 6, 2021

Methods that enable site selective acylation of sp

Язык: Английский

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Direct Enantioselective C(sp³)–H Acylation for the Synthesis of α-Amino Ketones

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(45), С. 19058 - 19064

Опубликована: Окт. 30, 2020

A direct enantioselective acylation of α-amino C(sp3)-H bonds with carboxylic acids has been achieved via the merger transition metal and photoredox catalysis. This straightforward protocol enables cross-coupling a wide range acids, one class feedstock chemicals, readily available N-alkyl benzamides to produce highly valuable ketones in high enantioselectivities under mild conditions. The synthetic utility this method is further demonstrated by gram scale synthesis application late-stage functionalization. provides an unprecedented solution address challenging stereocontrol metallaphotoredox catalysis Mechanistic studies suggest α-C(sp3)-H bond benzamide coupling partner cleavage photocatalytically generated bromine radicals form alkyl radicals, which subsequently engages nickel-catalyzed asymmetric acylation.

Язык: Английский

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Site-Selective Direct C–H Pyridylation of Unactivated Alkanes by Triplet Excited Anthraquinone

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(7), С. 3003 - 3012

Опубликована: Фев. 8, 2021

Site-selective C-H functionalization in chemical feedstocks is a challenging and useful reaction the broad field of research. Here, we report modular photochemical platform for site-selective pyridylation unactivated hydrocarbons via unique synergistic effects triplet excited anthraquinone an amidyl radical-based reverse hydrogen atom transfer (RHAT) agent. The selective tertiary secondary C(sp3)-H bonds abundant was achieved by employing various N-aminopyridinium salts highly fashion, thus providing new catalytic system direct construction high-value-added compounds under ambient conditions. Moreover, this operationally simple protocol applicable to variety linear-, branched-, cyclo-alkanes more complex molecules with high degrees site selectivity visible-light conditions, which provides rapid straightforward access versatile synthons upgrading mild, metal-free

Язык: Английский

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A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июнь 29, 2021

Abstract Hydrogen atom abstraction (HAT) from C( sp 3 )–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report photo-induced chemical oxidant-free cross-dehydrogenative coupling (CDC) between heteroarenes using catalytic chloride cobalt catalyst. Couplings strong bond-containing substrates complex heteroarenes, have been achieved with satisfactory yields. This dual platform features situ engendered chlorine exploits cobaloxime catalyst to enable hydrogen evolution turnover. The practical value this protocol was demonstrated by gram-scale synthesis alkylated heteroarene merely equiv. loading.

Язык: Английский

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Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(2), С. 1045 - 1055

Опубликована: Янв. 5, 2022

Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides the C(sp2) coupling partner, variety aliphatic radical sources have been investigated. In principle, reactions enable access to same product scaffolds, but it can be hard discern which method because nonstandardized sets are used in scope evaluation. Herein, we report Ni/photoredox-catalyzed (deutero)methylation and alkylation halides where benzaldehyde di(alkyl) acetals serve alcohol-derived sources. Reaction development, mechanistic studies, late-stage derivatization biologically relevant chloride, fenofibrate, presented. Then, describe integration data science techniques, including DFT featurization, dimensionality reduction, hierarchical clustering, delineate diverse succinct collection that is representative chemical space substrate class. By superimposing examples from published on this space, identify areas sparse coverage high versus low average yields, enabling comparisons between prior art new method. Additionally, demonstrate systematically selected quantify population-wide reactivity trends reveal possible functional group incompatibility with supervised machine learning.

Язык: Английский

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