Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1543 - 1625

Published: Oct. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Language: Английский

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Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(17), P. 9790 - 9833

Published: Aug. 6, 2020

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides point that "flight tyranny tin" radical processes was considered for long time an unavoidable issue. This review summarizes main alternative approaches unstabilized radicals, using photons as traceless promoters. The recent development photochemical and photocatalyzed enabled discovery plethora new precursors, opening world chemistry broader community, thus allowing era photon democracy.

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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Transition Metal-Catalyzed Organic Reactions under Visible Light: Recent Developments and Future Perspectives

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(16), P. 9170 - 9196

Published: July 20, 2020

The development of transition metal (TM) catalysis for organic synthesis under visible light without recourse to typical photoredox catalysts has become a rapidly growing area research and been actively explored in the past several years. Distinct from extensively developed catalysis, which photocatalyst generally does not directly participate bond-forming process, photocatalyst/TM synergistic absorbs photon energy transfers TM catalyst through redox or transfer this Review focuses on summarizing recent developments photocatalytic reactions that use complexes both absorb catalytic bond formation involving covalently bonded intermediate. contents are categorized by used (Pd, Cu, Co, Ni, Mn, Au, Rh, Fe, Ru), with descending sequence according number examples reported each metal, provide an overview April 2020. Future perspectives personal opinions regarding expanding field also discussed.

Language: Английский

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Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(10), P. 2518 - 2531

Published: May 6, 2021

ConspectusCarbon dioxide (CO2) is not only a greenhouse gas and common waste product but also an inexpensive, readily available, renewable carbon resource. It important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization challenging owing to thermodynamic stability kinetic inertness. Although significant progress has been achieved, many limitations remain this field with regard substrate scope, reaction system, activation strategies.Since 2015, our group focused on CO2 synthesis. We are interested vast possibilities radical chemistry, although high reactivity radicals presents challenges controlling selectivity. hope develop highly useful transformations involving by achieving balance selectivity under mild conditions. Over past 6 years, we along other experts have disclosed radical-type carboxylative cyclizations carboxylations using CO2.We initiated research realizing Cu-catalyzed oxytrifluoromethylation allylamines heteroaryl methylamines generate 2-oxazolidones various precursors. Apart from Cu catalysis, visible-light photoredox catalysis powerful method achieve efficient cyclization. In these cases, single-electron-oxidation-promoted C–O bond formation between benzylic carbamates key step.Since carboxylic acids exist widely natural products bioactive drugs serve as bulk chemicals industry, realized further visible-light-promoted construct such chemicals. achieved selective umpolung imines, enamides, tetraalkylammonium salts, oxime esters successive single-electron-transfer (SSET) reduction. Using strategy, dearomative arylcarboxylation indoles CO2. addition incorporation 1 equiv per substrate, recently developed photoredox-catalyzed dicarboxylation alkenes, allenes, (hetero)arenes via SSET reduction, which allows two molecules into compounds diacids polymer precursors.In two-electron CO2, sought new strategies realize single-electron Inspired hypothetical electron-transfer mechanism iron–sulfur proteins, visible-light-driven thiocarboxylation alkenes catalytic iron salts promoters. The in-situ-generated Fe/S complexes likely able reduce anion, could react give stabilized radical. Moreover, charge-transfer complex (CTC) thiolate acrylate/styrene hydrocarboxylation generation or alkene anion. On basis novel CTC, organocatalytic Hantzsch ester effective reductant.

Language: Английский

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Catalysis with Palladium Complexes Photoexcited by Visible Light

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(34), P. 11586 - 11598

Published: Jan. 2, 2019

Abstract Palladium catalysis induced by visible light is an emerging field of catalysis. In contrast to classical reactions catalyzed Pd complexes in the ground state, which mostly proceed through two‐electron redox processes, mechanisms these new methods based on photoexcited usually operate transfer a single electron. Such processes lead putative hybrid Pd/radical species, exhibit both radical and Pd‐type reactivity. This Minireview highlights recent progress this rapidly growing area.

Language: Английский

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Three-Component, Interrupted Radical Heck/Allylic Substitution Cascade Involving Unactivated Alkyl Bromides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(22), P. 10173 - 10183

Published: May 7, 2020

Developing efficient and selective strategies to approach complex architectures containing (multi)stereogenic centers has been a long-standing synthetic challenge in both academia industry. Catalytic cascade reactions represent powerful means of rapidly leveraging molecular complexity from simple feedstocks. Unfortunately, carrying out Heck-type involving unactivated (tertiary) alkyl halides remains an unmet owing unavoidable β-hydride elimination. Herein, we show that modular, practical, general palladium-catalyzed, radical three-component coupling can indeed overcome the aforementioned limitations through interrupted Heck/allylic substitution sequence mediated by visible light. Selective 1,4-difunctionalization 1,3-dienes, such as butadiene, achieved employing different commercially available nitrogen-, oxygen-, sulfur-, or carbon-based nucleophiles bromides (>130 examples, mostly >95:5 E/Z, >20:1 rr). Sequential C(sp3)–C(sp3) C–X (N, O, S) bonds have constructed efficiently with broad scope high functional group tolerance. The flexibility versatility strategy illustrated gram-scale reaction streamlined syntheses ether, sulfone, tertiary amine products, some which would be difficult access via currently established methods.

Language: Английский

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Visible Light-Induced Excited-State Transition-Metal Catalysis

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(5), P. 510 - 523

Published: June 1, 2019

Language: Английский

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Visible‐Light‐Driven, Copper‐Catalyzed Decarboxylative C(sp³)−H Alkylation of Glycine and Peptides

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(48), P. 15841 - 15846

Published: Oct. 8, 2018

Despite a well-developed and growing body of work in Cu catalysis, the potential to serve as photocatalyst remains underexplored. Reported herein is first example visible-light-induced Cu-catalyzed decarboxylative C(sp3 )-H alkylation glycine for preparing α-alkylated unnatural α-amino acids. It merits mentioning that mild conditions good functional-group tolerance allow modification peptides using this method. The mechanistic studies revealed radical-radical coupling pathway involved reaction.

Language: Английский

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Catalytic radical generation of π-allylpalladium complexes

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(4), P. 393 - 400

Published: March 23, 2020

Language: Английский

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