Photocatalysis in organic and polymer synthesis

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(22), P. 6165 - 6212

Published: Jan. 1, 2016

This review, with over 600 references, summarizes the recent applications of photoredox catalysis for organic transformation and polymer synthesis.

Language: Английский

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Free Radical Chemistry Enabled by Visible Light-Induced Electron Transfer

Accounts of Chemical Research, Journal Year: 2016, Volume and Issue: 49(10), P. 2295 - 2306

Published: Aug. 16, 2016

ConspectusHarnessing visible light as the driving force for chemical transformations generally offers a more environmentally friendly alternative compared with classical synthetic methodology. The transition metal-based photocatalysts commonly employed in photoredox catalysis absorb efficiently spectrum, unlike most organic substrates, allowing orthogonal excitation. subsequent excited states are both reducing and oxidizing than ground state catalyst competitive some of powerful single-electron oxidants or reductants available to chemists yet simply accessed via irradiation. benefits this strategy have proven particularly useful radical chemistry, field that traditionally employs rather toxic hazardous reagents generate desired intermediates.In Account, we discuss our efforts leverage radical-based bond-forming bond-cleaving events which few, if any, benign alternatives exist. Mechanistic investigations driven contributions field, facilitating offering new, unexpected opportunities. In fact, total synthesis (+)-gliocladin C was only possible upon elucidating propensity various trialkylamine additives elicit dual behavior reductive quencher H-atom donor. Importantly, while natural product central initial motivations explore these photochemical processes, since demonstrated applicability within other subfields evaluation flow technologies demonstrates potential translate results from bench pilot scale.Our forays into began fundamental methodology, providing tin-free dehalogenation exchanged gamut previously such transformation light-mediated, ambient temperature conditions. Evolving work, new avenue toward atom transfer addition (ATRA) chemistry developed, enabling functionalization double triple bonds. also expanded portfolio target clinically relevant scaffolds. Photoredox proved effective generating high value fluorinated alkyl radicals through use abundantly starting materials, access libraries trifluoromethylated (hetero)arenes well intriguing gem-difluoro benzyl motifs novel Smiles rearrangement. Finally, sustainable lignin processing selective C–O bond cleavage collection is meant highlight light-mediated impact variety industrial sectors.

Language: Английский

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Photochemical Generation of Nitrogen-Centered Amidyl, Hydrazonyl, and Imidyl Radicals: Methodology Developments and Catalytic Applications

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(8), P. 4999 - 5022

Published: June 19, 2017

During the past decade, visible light photocatalysis has become a powerful synthetic platform for promoting challenging bond constructions under mild reaction conditions. These photocatalytic systems rely on harnessing energy purposes through generation of reactive but controllable free radical species. Recent progress in area established it as an enabling catalytic strategy and selective nitrogen-centered radicals. The application activation amides, hydrazones, imides represents valuable approach facilitating formation Within span only couple years, significant been made expediting amidyl, hydrazonyl, imidyl radicals from variety precursors. This Perspective highlights recent advances light-mediated these A particular emphasis is placed unique ability accessing elusive manifolds construction diversely functionalized nitrogen-containing motifs nontraditional disconnections contemporary chemistry.

Language: Английский

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Visible Light Photocatalysis: Applications and New Disconnections in the Synthesis of Pharmaceutical Agents

Organic Process Research & Development, Journal Year: 2016, Volume and Issue: 20(7), P. 1134 - 1147

Published: June 1, 2016

Photoredox catalysis has emerged as a powerful tool for the synthetic chemist to access challenging targets and generate new structural complexity. This review focuses on application of this mode arrive at known pharmaceutically active compounds. Within setting, growing synergy with other modes catalysis, such nickel/photoredox dual well pioneering examples utilizing continuous flow transition photoredox preparative scale will be highlighted.

Language: Английский

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Photocatalysis in the Life Science Industry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

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Distal radical migration strategy: an emerging synthetic means

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 47(3), P. 654 - 667

Published: Nov. 27, 2017

The remote radical migration strategy has gained considerable momentum. During the past three years, we have witnessed rapid development of sustainable and practical C-C C-H bond functionalization by means long-distance 1,n-radical (n = 4, 5, 6) events. Its advent brings our chemical community a new platform to deal with challenging transformations thus complements existing ionic-type protocols. In this review, recent achievements in distal triggered are summarized.

Language: Английский

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Arylsulfonylacetamides as bifunctional reagents for alkene aminoarylation

Science, Journal Year: 2018, Volume and Issue: 361(6409), P. 1369 - 1373

Published: Sept. 28, 2018

Alkene aminoarylation with a single, bifunctional reagent is concise synthetic strategy. We report catalytic protocol for the addition of arylsulfonylacetamides across electron-rich alkenes complete anti-Markovnikov regioselectivity and excellent diastereoselectivity to provide 2,2-diarylethylamines. In this process, single-electron alkene oxidation enables carbon-nitrogen bond formation key benzylic radical poised Smiles-Truce 1,5-aryl shift. This reaction redox-neutral, exhibits broad functional group compatibility, occurs at room temperature loss sulfur dioxide. As process driven by visible light, uses readily available starting materials, demonstrates convergent synthesis, it well suited use in variety endeavors.

Language: Английский

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Radical cascade reactions triggered by single electron transfer

Nature Reviews Chemistry, Journal Year: 2017, Volume and Issue: 1(10)

Published: Oct. 4, 2017

Language: Английский

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Catalytic Defluoroalkylation of Trifluoromethylaromatics with Unactivated Alkenes

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 140(1), P. 163 - 166

Published: Dec. 19, 2017

We describe a new catalytic approach to selective functionalization of the strong C-F bonds in trifluoromethylaromatic (Ar-CF3) systems. In this approach, single electron reduction Ar-CF3 substrates (using photoredox catalyst) results difluorobenzylic radical formation through cleavage mechanism. These radicals undergo efficient intermolecular coupling with simple alkenes defluoroalkylation process where termination is accomplished by polarity reversal catalyst. This mild protocol engages wide range give medicinally relevant fluorinated substructures complete regiocontrol.

Language: Английский

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A Brief Introduction to Chemical Reaction Optimization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(6), P. 3089 - 3126

Published: Feb. 23, 2023

From the start of a synthetic chemist's training, experiments are conducted based on recipes from textbooks and manuscripts that achieve clean reaction outcomes, allowing scientist to develop practical skills some chemical intuition. This procedure is often kept long into researcher's career, as new developed similar protocols, intuition-guided deviations through learning failed experiments. However, when attempting understand systems interest, it has been shown model-based, algorithm-based, miniaturized high-throughput techniques outperform human intuition optimization in much more time- material-efficient manner; this covered detail paper. As many chemists not exposed these undergraduate teaching, leads disproportionate number scientists wish optimize their reactions but unable use methodologies or simply unaware existence. review highlights basics, cutting-edge, modern well its relation process scale-up can thereby serve reference for inspired each techniques, detailing several respective applications.

Language: Английский

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