Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1485 - 1542

Опубликована: Ноя. 18, 2021

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox combined unparalleled capacity for bond formation broad utility photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation allowed engagement simple starting materials metal-mediated bond-forming Moreover, electron or energy transfer directly key organometallic intermediates provided novel modes entirely complementary to traditional catalytic platforms. This Review details contextualizes advancements molecule construction brought forth by metallaphotocatalysis.

Язык: Английский

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Mechanisms of Nickel-Catalyzed Cross-Coupling Reactions

Trends in Chemistry, Год журнала: 2019, Номер 1(9), С. 830 - 844

Опубликована: Сен. 13, 2019

Язык: Английский

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Advances in theE → ZIsomerization of Alkenes Using Small Molecule Photocatalysts

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2650 - 2694

Опубликована: Авг. 27, 2021

Geometrical E → Z alkene isomerization is intimately entwined in the historical fabric of organic photochemistry and enjoying a renaissance (Roth et al. Angew. Chem., Int. Ed. Engl. 1989 28, 1193–1207). This consequence fundamental stereochemical importance Z-alkenes, juxtaposed with frustrations thermal reactivity that are rooted microscopic reversibility. Accessing excited state paradigms allow this latter obstacle to be circumnavigated by exploiting subtle differences photophysical behavior substrate product chromophores: provides molecular basis for directionality. While direct irradiation operationally simple, photosensitization via selective energy transfer enables augmentation repertoire include substrates not directly photons. Through sustained innovation, an impressive portfolio tailored small molecule catalysts range triplet energies now widely available facilitate contra-thermodynamic thermo-neutral reactions generate Z-alkene fragments. review intended serve as practical guide covering geometric alkenes enabled catalysis from 2000 2020, logical sequel excellent treatment Dugave Demange (Chem. Rev. 2003 103, 2475–2532). The mechanistic foundations underpinning selectivity discussed together induction models rationales explain counterintuitive directionality these processes which very distinguish product. Implications subsequent stereospecific transformations, application total synthesis, regioselective polyene isomerization, spatiotemporal control pre-existing configuration broader sense discussed.

Язык: Английский

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Recent advances in photoredox and nickel dual-catalyzed cascade reactions: pushing the boundaries of complexity

Chemical Science, Год журнала: 2020, Номер 11(16), С. 4051 - 4064

Опубликована: Янв. 1, 2020

Cascade reactions that produce multiple chemical bonds in one synthetic operation are important the efficient construction of complex molecules.

Язык: Английский

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Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Год журнала: 2021, Номер 50(19), С. 10836 - 10856

Опубликована: Янв. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Язык: Английский

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Developments in Photoredox/Nickel Dual-Catalyzed 1,2-Difunctionalizations

Chem, Год журнала: 2020, Номер 6(6), С. 1327 - 1339

Опубликована: Июнь 1, 2020

Язык: Английский

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Stereoinduction in Metallaphotoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(4), С. 1714 - 1726

Опубликована: Июль 17, 2020

Metallaphotoredox catalysis has evolved into an enabling platform to construct C(sp3 )-hybridized centers under remarkably mild reaction conditions. The cultivation of abundant radical precursor feedstocks significantly increased the scope transition-metal-catalyzed cross-couplings, especially with respect C(sp2 )-C(sp3 ) linkages. In recent years, considerable effort been devoted understanding origin stereoinduction in dual catalytic processes. this context, Ni- and Cu-catalyzed transformations have played a predominant role exploiting mode catalysis. Herein, we provide critical overview on progress enantioselective bond formations enabled by manifolds. Furthermore, selected stereochemical control elements within realm diastereoselective are discussed.

Язык: Английский

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Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 4162 - 4184

Опубликована: Янв. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Язык: Английский

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Remote Nickel-Catalyzed Cross-Coupling Arylation via Proton-Coupled Electron Transfer-Enabled C–C Bond Cleavage

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(7), С. 3532 - 3539

Опубликована: Фев. 4, 2020

Cross-coupling reactions for carbon–carbon and carbon–heteroatom bond formation are of great importance in modern chemical synthesis. In addition to classical cross-couplings involving preformed or preactivated coupling partners, more recently breakthroughs have been made the selective, direct abundant aliphatic carbon–hydrogen bonds using hydrogen atom transfer which bond-dissociation energy is thermodynamic driving force. The challenging activation still rather underdeveloped due inertness. Herein, we report a mild general strategy diverse set readily available cyclic alcohols remote site-specific arylation ketones via combination photoredox-mediated multisite concerted proton–electron (MS-PCET) nickel catalysis. current cross-coupling proceeds with generation an alkoxy radical utilizing free (BDFE) as Subsequently, resulting carbon-centered radicals formed by C–C cleavage merge catalytic cycle create C(sp3)–C(sp2) bonds.

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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