Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1485 - 1542

Published: Nov. 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.

Language: Английский

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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7587 - 7680

Published: Jan. 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.

Language: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

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Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

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Transition metal-catalysed allylic functionalization reactions involving radicals

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(17), P. 6186 - 6197

Published: Jan. 1, 2020

In this tutorial review, different types of transition metal-catalysed allylic functionalization reactions involving radicals are highlighted.

Language: Английский

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Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13382 - 13392

Published: Aug. 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.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(22), P. 12808 - 12827

Published: Jan. 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.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(11), P. 4168 - 4173

Published: March 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.

Language: 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, Journal Year: 2021, Volume and Issue: 60(42), P. 22956 - 22962

Published: Aug. 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.

Language: Английский

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