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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Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2292 - 2352

Опубликована: Дек. 9, 2021

The halogen-atom transfer (XAT) is one of the most important and applied processes for generation carbon radicals in synthetic chemistry. In this review, we summarize highlight aspects associated with XAT impact it has had on photochemistry photocatalysis. organization material starts analysis mechanistic then follows a subdivision based nature reagents used halogen abstraction. This review aims to provide general overview fundamental concepts main agents involved objective offering tool understand facilitate development new radical strategies.

Язык: Английский

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New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Год журнала: 2020, Номер 6(8), С. 1317 - 1340

Опубликована: Июль 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

Язык: Английский

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

Chemical Reviews, Год журнала: 2020, Номер 120(17), С. 9790 - 9833

Опубликована: Авг. 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.

Язык: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

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

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 766 - 897

Опубликована: Дек. 22, 2020

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

Язык: Английский

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(18), С. 8122 - 8129

Опубликована: Апрель 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Язык: Английский

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Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis

ChemCatChem, Год журнала: 2022, Номер 14(19)

Опубликована: Авг. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Язык: Английский

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Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(49), С. 20661 - 20670

Опубликована: Ноя. 24, 2020

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated variety of alkene functionalization reactions, most which proceed via an anodic oxidation pathway. In this report, we further expand the scope electrochemistry reductive alkenes. particular, strategic choice reagents reaction conditions enabled radical-polar crossover pathway wherein two distinct electrophiles can be added across highly chemo- regioselective fashion. Specifically, used strategy intermolecular carboformylation, anti-Markovnikov hydroalkylation, carbocarboxylation alkenes—reactions with rare precedents literature—by means electroreductive generation alkyl radical carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) simple, transition-metal-free display broad substrate good tolerance functional groups. A uniform protocol achieve all three transformations by simply altering medium. development provides new avenue for constructing Csp3–Csp3 bonds.

Язык: Английский

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