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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Visible light-mediated photolysis of organic molecules: the case study of diazo compounds

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(48), P. 7346 - 7360

Published: Jan. 1, 2023

This article discusses the photochemistry of several diazo compounds undergoing visible light-mediated photolysis to generate free carbenes (or other highly reactive intermediates), which can be sequentially trapped by different reacting partners.

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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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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Photocatalytic Synthesis of Indanone, Pyrone, and Pyridinone Derivatives with Diazo Compounds as Radical Precursors

Organic Letters, Journal Year: 2024, Volume and Issue: 26(7), P. 1393 - 1398

Published: Feb. 12, 2024

We disclose herein a photocatalytic radical cascade cyclization of diazoalkanes for the divergent synthesis important carbocycles and heterocycles. Under optimal reaction conditions, various indanone, pyrone, pyridinone derivatives can be obtained in moderate to good yields. Mechanistic experiments support formation carbon-centered radicals from through proton-coupled electron transfer process. Scale-up using continuous flow technology useful downstream application formed heterocycles further render strategy attractive valuable.

Language: Английский

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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11851 - 11856

Published: Aug. 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.

Language: Английский

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Photochemical multicomponent transformation of acceptor-only diazoalkanes by merging their cycloaddition and carbene reactivities

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(9), P. 108335 - 108335

Published: March 15, 2023

Language: Английский

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Unveiling catalyst-free electro-photochemical reactivity of aryl diazoesters and facile synthesis of oxazoles, imide-fused pyrroles and tetrahydro-epoxy-pyridines via carbene radical anions

Chemical Science, Journal Year: 2023, Volume and Issue: 14(23), P. 6216 - 6225

Published: Jan. 1, 2023

First ever catalyst-free electro-photochemical generation of carbene radical anion from aryl diazoester with direct application into synthesis interesting N-heterocycles broad substrate scope and excellent diastereo-selectivity.

Language: Английский

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Recent Advances in Radical Reactions of Azo Compounds

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1565 - 1579

Published: April 12, 2023

Abstract Azo compounds have attracted much attention in the past decades, due to their unique properties. Recently, free radical strategy has been widely applied chemical transformations of azobenzenes, dialkyl azodicarboxylates, mainly including hydrogenation and functionalization N=N double bond, N ‐functionalization reactions via cleavage bonds. In this review, we systematically summarized these as well mechanisms are discussed. magnified image

Language: Английский

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Divergent Synthesis of Trifluoromethyl-Substituted 1,2-Dihydroquinoxalines and Diimines by Cascade Reactions of CF₃–Imidoyl Sulfoxonium Ylides with Azo Compounds

Organic Letters, Journal Year: 2023, Volume and Issue: 25(38), P. 7046 - 7050

Published: Sept. 18, 2023

A base-mediated cascade reaction of CF3-imidoyl sulfoxonium ylides and azo compounds has been achieved, allowing for facile access to trifluoromethyl-substituted 1,2-dihydroquinoxalines diimines in moderate excellent yields. Noteworthy is that the unusual N-N bond cleavage rearrangement are involved transformations.

Language: Английский

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