Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7214 - 7261

Опубликована: Май 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.

Язык: Английский

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

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9806 - 9816

Опубликована: Июль 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.

Язык: Английский

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Cross-Coupling of Amines via Photocatalytic Denitrogenation of In Situ Generated Diazenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11524 - 11529

Опубликована: Май 18, 2023

A method for C(sp

Язык: Английский

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Catalytic Olefin Cyclopropanation with In Situ-Generated Dialkyl Diazomethanes via Co(II)-Based Metalloradical Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(17), С. 11851 - 11856

Опубликована: Авг. 23, 2023

The synthesis of dialkyl-substituted cyclopropanes is an important challenge in with applications drug discovery and agrochemistry. Herein, we report on the gem-dialkyl situ-generated dialkyl diazo compounds under Bamford–Stevens conditions. A simple cobalt catalyst was identified to be optimal achieve high yields. Experimental computational studies suggest participation a metalloradical reaction mechanism that facilitates carbene transfer reactions provides access single step.

Язык: Английский

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Photogenerated donor–donor diazo compounds enable facile access to spirocyclopropanes

Chemical Communications, Год журнала: 2023, Номер 59(79), С. 11835 - 11838

Опубликована: Янв. 1, 2023

Prompted by the increasing interest in strained hydrocarbons as potential drug candidates, we developed a simple and efficient photochemical protocol for (spiro)cyclopropanes from bench stable tosylhydrazones electron poor olefins. This two-step one-pot transformation proceeds (3+2)-cycloaddition of situ formed donor-donor diazo compounds, followed nitrogen extrusion Δ1-pyrazoline intermediates. Notably, kinetic analysis enabled isolation intermediary spiro-heterocycles.

Язык: Английский

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Unlocking the reactivity of diazo compounds in red light with the use of photochemical tools

Chemical Communications, Год журнала: 2023, Номер 59(99), С. 14649 - 14652

Опубликована: Янв. 1, 2023

The red light-irradiation of structurally diversified diazoalkanes gives access to reactive intermediates via direct photolysis and photosensitization or photoredox approaches.

Язык: Английский

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The efficient synthesis of three-membered rings via photo- and electrochemical strategies

Chemical Science, Год журнала: 2024, Номер 15(34), С. 13576 - 13604

Опубликована: Янв. 1, 2024

Three-membered rings, such as epoxides, aziridines, oxaziridines, cyclopropenes, vinyloxaziridines, and azirines, are recognized crucial pharmacophores building blocks in organic chemistry drug discovery. Despite the significant advances synthesis of these rings through photo/electrochemical methods over past decade, there has currently been no focused discussion updated overviews on this topic. Therefore, we presented review article efficient three-membered using photo- electrochemical strategies, covering literature since 2015. In study, a conceptual overview detailed discussions were provided to illustrate advancement field. Moreover, brief outlines current challenges opportunities synthesizing strategies.

Язык: Английский

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Facile Access to Hindered Ethers via Photoinduced O–H Bond Insertions

ACS Central Science, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

The synthesis of the hindered and polyfluorinated dialkyl ethers poses challenges owing to bulkiness tertiary alcohols low nucleophilicity alcohols. Additionally, associated competitive side reactions always provide poor reactivities. Although certain strategies, such as electrocatalytic decarboxylation hydroalkoxylation, have been explored, a straightforward method for obtaining with structural diversity remains elusive. In this study, we exploited photoinduced approach that involves in situ formation singlet carbenes followed by O-H insertions access congested or Moreover, other nucleophiles phenols, H2O, thiols, silanols, tributyltin hydride, etc., are also tolerable obtain valuable products. gram-scale marketed drugs modification complex molecules demonstrate practicality approach. detailed mechanistic studies elucidated key intermediates reaction mechanism, which were distinct from traditional metal-carbenoid insertions.

Язык: Английский

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Recent advances of 9-fluorenone in photoredox catalysis

Molecular Catalysis, Год журнала: 2025, Номер 582, С. 115169 - 115169

Опубликована: Май 8, 2025

Язык: Английский

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Oxadiazolines as Photoreleasable Labels for Drug Target Identification

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 17, 2024

Photoaffinity labeling is a widely used technique for studying ligand-protein and protein-protein interactions. Traditional photoaffinity labels utilize nonspecific C-H bond insertion reactions mediated by highly reactive intermediate. Despite being the most labels, diazirines exhibit limited compatibility with downstream organic suffer from storage stability concerns. This study introduces oxadiazolines as innovative complementary photoactivatable addition to toolbox demonstrates their application in vitro through

Язык: Английский

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