Photochemical and electrochemical strategies in C–F bond activation and functionalization

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 9(3), P. 853 - 873

Published: Dec. 7, 2021

The recent advances in photochemical or electrochemical C–F bond activation and functionalization have been summarized discussed.

Language: Английский

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Unlocking novel reaction pathways of diazoalkanes with visible light

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(17), P. 2788 - 2798

Published: Jan. 1, 2022

In this feature article, the photolysis and dye-sensitized reactions of diazoalkanes are discussed applications in organic synthesis presented.

Language: Английский

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Photocatalytic C(sp³) radical generationviaC–H, C–C, and C–X bond cleavage

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5465 - 5504

Published: Jan. 1, 2022

C(sp 3 ) radicals (R˙) are of broad research interest and synthetic utility.

Language: Английский

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Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7214 - 7261

Published: May 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Language: Английский

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Photodriven Radical-Polar Crossover Cyclization Strategy: Synthesis of Pyrazolo[1,5-a]pyridines from Diazo Compounds

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2511 - 2516

Published: March 20, 2024

This work demonstrates the synthesis of a variety perfluoroalkyl heterocycles via visible-light-driven radical-polar crossover cyclization strategy. In this process, single-electron reduction/SNV-type/cyclization sequences follow radical addition reaction diazoester, which differs from current role diazoesters as precursors/acceptors. transformation excellent functional group compatibility and allows for modification many bioactive molecules with diazoesters. Such could represent novel approach to photochemical diazo compounds.

Language: Английский

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Photocatalytic gem‐Difluoroolefination Reactions by a Formal C−C Coupling/Defluorination Reaction with Diazoacetates

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(4)

Published: Oct. 30, 2021

The photolysis of diazoalkanes to conduct singlet carbene transfer reactions colored has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access triplet intermediates via energy highly efficient gem-difluoroolefination with α-trifluoromethyl styrenes. use tertiary amines proved pivotal unlock this unusual reaction pathway and prevent undesired cyclopropanation pathways. amine further facilitates ultimate abstraction fluoride yield gem-difluoroolefins (43 examples, up 88 % yield), which is supported by experimental theoretical mechanistic studies. We explored synthesis method broad substrate scope, ranging from simple olefins heterocyclic towards decoration pharmaceutically relevant building blocks.

Language: Английский

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Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 6018 - 6023

Published: Aug. 10, 2022

We disclosed herein a straightforward photochemical method for the construction of phenanthridines containing synthetically useful succinate unit. The reaction occurred under visible-light irradiation with cheap eosin Y Na as photoredox catalyst and diazo compound precursor. Under optimal conditions, wide range were obtained in moderate to good yields. Note that units final heterocycles could be easily transformed into many valuable structures, such γ-butyrolactone, dihydrofuran-2(3H)-one, tetrahydrofuran. Mechanistic experiments performed support proposed mechanism.

Language: Английский

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Visible Light‐Mediated Cyclopropanation: Recent Progress

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(44)

Published: Oct. 21, 2022

Abstract Cyclopropanes are one of the most important strained rings existing in various pharmaceutical products and secondary metabolites. They also widely used total synthesis natural products, medicinal chemistry, materials science. In past years, photochemical cyclopropanation has been gradually developed as a robust attractive synthetic method to prepare diverse cyclopropane backbones. this review, we summarize recent advances visible light‐mediated synthesis, especially using carbene transfer strategy photocatalytic radical reactions.

Language: Английский

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Visible Light-Driven α-Diazoketones as Denitrogenated Synthons: Synthesis of Fluorinated N-Heterocycles via Multicomponent Cyclization Reactions

Organic Letters, Journal Year: 2023, Volume and Issue: 25(18), P. 3314 - 3318

Published: May 1, 2023

We disclose herein an efficient photochemical formal [3+2+1] annulation strategy for the transformation of diazocarbonyl compounds into various fluorinated nitrogen-containing heterocycles. This is characterized by reacting fluoroalkyl radicals with α-diazoketones, which are used as infrequent denitrogenated synthons under visible light. Moreover, a wide range N-heterocycles containing precious CF3 and perfluoroalkylated groups constructed in moderate to good yields. Notably, this may provide fruitful path synthesis complex organofluorides via diazo/fluorine/radical chemistry.

Language: Английский

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Visible-Light-Mediated Energy Transfer Enables Cyclopropanes Bearing Contiguous All-Carbon Quaternary Centers

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9806 - 9816

Published: July 11, 2023

Cyclopropanes bearing contiguous all-carbon quaternary centers continue to attract attention due their bioactivities. However, methods obtain cyclopropanes with remain largely unexplored the high steric hindrance of these compounds. Herein, we report a visible-light-mediated energy-transfer (EnT) strategy realize in situ donor/donor carbenes from readily available N-tosylhydrazones, facilitating synthesis highly congested EWG-free cyclopropanes. Through this approach, are rapidly installed into complex bioactive molecules, fluorescent and other useful building blocks that challenging synthesize. Detailed mechanistic reactions DFT studies clearly demonstrated role photosensitizer, formation carbenes, necessity light base system.

Language: Английский

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