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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Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

Chemical Society Reviews, Год журнала: 2021, Номер 50(13), С. 7587 - 7680

Опубликована: Янв. 1, 2021

Organic compounds that show Thermally Activated Delayed Fluorescence (TADF) have become wildly popular as next generation emitters in organic light-emitting diodes (OLEDs), but since 2016, received significant and increasing attention photocatalysts.

Язык: Английский

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Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 13382 - 13392

Опубликована: Авг. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Язык: Английский

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Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(11), С. 4168 - 4173

Опубликована: Март 11, 2021

1,3-Dienes are readily available feedstocks that widely used in the laboratory and industry. However, potential of converting 1,3-dienes into value-added products, especially chiral has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve first visible-light-induced, enantioselective carbocyanation by using carboxylic acid derivatives trimethylsilyl cyanide. Under mild neutral conditions, a diverse range allyl cyanides produced generally good efficiency with high enantioselectivity from bench-stable user-safe chemicals. Moreover, preliminary results also confirm this success can be expanded to 1,3-enynes four-component carbonylative 1,3-enynes.

Язык: Английский

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Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Coupling of 1,3‐Dienes: An Alternative to Kharasch–Sosnovsky Reaction

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(42), С. 22956 - 22962

Опубликована: Авг. 18, 2021

Abstract Kharasch–Sosnovsky reaction is one of the most powerful methods for allylic oxidation alkenes. However, inherent radical mechanism and use peroxides as both oxidants oxygen nucleophiles render dearth universal catalytic systems highly enantioselective variants limited scope. Herein, an alternative to asymmetric that utilized a chiral copper catalyst purple‐LED irradiation enable three‐component coupling 1,3‐dienes, oxime esters, carboxylic acids reported. This protocol features mild conditions, remarkable scope functional group tolerance evidenced by >80 examples utility in late‐stage modification pharmaceuticals natural products. Detailed mechanistic studies provide evidences radical‐based pathway.

Язык: Английский

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Recent advances in radical-mediated transformations of 1,3-dienes

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2022, Номер 43(3), С. 548 - 557

Опубликована: Фев. 2, 2022

Язык: Английский

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Multiplicative enhancement of stereoenrichment by a single catalyst for deracemization of alcohols

Science, Год журнала: 2023, Номер 382(6669), С. 458 - 464

Опубликована: Окт. 26, 2023

Stereochemical enrichment of a racemic mixture by deracemization must overcome unfavorable entropic effects as well the principle microscopic reversibility; recently, photochemical reaction pathways unveiled energetic input light have led to innovations toward this end, most often ablation stereogenic C(sp3)-H bond. We report photochemically driven protocol in which single chiral catalyst two mechanistically different steps, C-C bond cleavage and formation, achieve multiplicative enhancement stereoinduction, leads high levels stereoselectivity. Ligand-to-metal charge transfer excitation titanium coordinated phosphoric acid or bisoxazoline efficiently enriches alcohols that feature adjacent fully substituted centers enantiomeric ratios up 99:1. Mechanistic investigations support pathway sequential radical-mediated scission formation through common prochiral intermediate reveal that, although overall stereoenrichment is high, selectivity each individual step moderate.

Язык: Английский

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Hantzsch Esters Enabled [2π+2σ] Cycloadditions of Bicyclo [1.1.0] butanes and Alkenes under Photo Conditions

Organic Letters, Год журнала: 2023, Номер 25(45), С. 8116 - 8120

Опубликована: Ноя. 8, 2023

Hantzsch esters (HEs) are widely recognized as sources of hydride ions (H-) and sacrificial electron donors in their ground state. Here, we report the application HE a mediator [2π+2σ] cycloaddition bicyclo[1.1.0]butanes (BCBs) with alkenes under photo conditions. Through this strategy, various substituted bicyclo[2.1.1]hexanes can be efficiently prepared.

Язык: Английский

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Photoinduced Pd-Catalyzed Enantioselective Carboamination of Dienes via Aliphatic C–H Bond Elaboration

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 12053 - 12062

Опубликована: Апрель 16, 2024

Three-component diene carboaminations offer a potent means to access synthetically valuable allylic amines with rapid molecular complexity escalation. The existing literature primarily discloses racemic examples, necessitating the use of halides/pseudohalides as substrates. This paper introduces photoinduced Pd-catalyzed enantioselective three-component carboamination aryl-substituted 1,3-dienes, leveraging aliphatic C–H bonds for synthesis. reaction employs 10 mol % chiral palladium catalyst and an excess aryl bromide HAT reagent. approach yields diverse allylamines moderate excellent enantioselectivities. Notably, it stands first instance asymmetric reaction, directly utilizing abundant C(sp3)–H bearing partners, such toluene-type substrates, ethers, amines, esters, ketones. protocol exhibits versatility across encompassing aliphatic, aromatic, primary, secondary derivatives. method could serve versatile platform stereoselective incorporation various nucleophiles, dienes, partners.

Язык: Английский

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The Golden Age of Thermally Activated Delayed Fluorescence Materials: Design and Exploitation

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Дек. 12, 2024

Since the seminal report by Adachi and co-workers in 2012, there has been a veritable explosion of interest design thermally activated delayed fluorescence (TADF) compounds, particularly as emitters for organic light-emitting diodes (OLEDs). With rapid advancements innovation materials design, efficiencies TADF OLEDs each primary color points well white devices now rival those state-of-the-art phosphorescent emitters. Beyond electroluminescent devices, compounds have also found increasing utility applications numerous related fields, from photocatalysis, to sensing, imaging beyond. Following our previous review 2017 (

Язык: Английский

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