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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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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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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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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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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Synthesis and applications of sodium sulfinates (RSO₂Na): a powerful building block for the synthesis of organosulfur compounds

RSC Advances, Год журнала: 2021, Номер 11(16), С. 9130 - 9221

Опубликована: Янв. 1, 2021

This review provides a unique and comprehensive overview of sodium sulfinates for synthesizing many valuable sulfur-containing compounds, such as thiosulfonates, sulfonamides, sulfides, sulfones, allyl vinyl sulfones β-keto sulfones.

Язык: Английский

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Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention

Chemical Society Reviews, Год журнала: 2021, Номер 50(22), С. 12808 - 12827

Опубликована: Янв. 1, 2021

Transition metal-catalysed asymmetric coupling has been established as a robust tool for constructing complex organic molecules. Although this area extensively studied, the development of efficient protocols to construct stereogenic centres with excellent regio- and enantioselectivities is highly desirable remains challenging. Asymmetric transition metal catalysis light intervention provides practical alternative strategy current methods considerably expands synthetic utility result abundant feedstocks mild conditions. This tutorial review comprehensively summarizes recent advances in transition-metal-catalysed reactions intervention; particular, concise analysis substrate scope mechanistic scenarios governing stereocontrol discussed.

Язык: Английский

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Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Фев. 4, 2022

Abstract The synthesis of all-carbon tetrasubstituted olefins under mild reaction conditions is challenging because the inevitable issues including significant steric hindrance and uncontrolled Z/E stereoselectivity. In this paper, we report alkenes from readily available carboxylic acids alkenyl triflates with synergistic catalysis cyclo-octa-1,5-diene(tetramethyl-1,4-benzoquinone)nickel visible light an air atmosphere, thus avoiding need for a glovebox or Schlenk line. A wide range aromatic cyclic acyclic undergo C-C coupling process smoothly, forming structurally diverse stereospecifically in moderate to good yields. practicality method further illustrated by late-stage modification complex molecules, one pot gram-scale applications. This important step towards valuable utilization acids, it also simplifies experimental operation metallophotoredox moisture sensitive nickel(0) catalysis.

Язык: Английский

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