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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Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

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Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(12), P. 2586 - 2591

Published: Dec. 11, 2019

The photolysis of diazoalkanes is a timely strategy to conduct carbene-transfer reactions under mild and metal-free reaction conditions, has developed as an important alternative conventional metal-catalyzed reactions. One the major limitations lies within rapidly occurring side carbene intermediate with remaining diazoalkane molecules that result in use excess partner thus impacts on efficiency. Herein, we describe protocol takes advantage situ generation donor-acceptor by Bamford-Stevens reaction. Following this strategy, concentration can be minimized reduce unwanted now photochemical transfer stoichiometric conditions. We have explored approach C-H N-H functionalization cyclopropanation N-heterocycles could demonstrate applicability method 51 examples.

Language: Английский

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Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes

Chemical Science, Journal Year: 2022, Volume and Issue: 13(11), P. 3273 - 3280

Published: Jan. 1, 2022

Visible light induced singlet nucleophilic carbenes undergo rapid [2 + 1]-cycloaddition with tethered olefins to afford unique bicyclo[3.1.0]hexane and bicyclo[4.1.0]heptane scaffolds. This cyclopropanation process requires only visible irradiation proceed, circumventing the use of exogenous (photo)catalysts, sensitisers or additives showcases a vastly underexplored mode reactivity for in chemical synthesis. The discovery additional transformations including cyclopropanation/retro-Michael/Michael cascade chromanones photochemical C-H insertion reaction are also described.

Language: Английский

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Divergent C(sp²)–H arylation of heterocycles via organic photoredox catalysis

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(7), P. 3017 - 3022

Published: Jan. 1, 2022

Introducing aryl moieties into heterocyclic scaffolds is a key step in the syntheses of natural products, drugs, and functional materials.

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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Recent progress in the application of iodonium ylides in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 6999 - 7015

Published: Jan. 1, 2022

This review summarizes the recent advances in synthetic application of iodonium ylides covering 2017 to 2022.

Language: Английский

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A Spiro Phosphamide Catalyzed Enantioselective Proton Transfer of Ylides in a Free Carbene Insertion into N−H Bonds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 14, 2023

Free carbene readily causes multiple side reactions due to its high energy, thus asymmetric transformation is very difficult. We present here our findings of high-pKa Brønsted acid catalysts that enable free insertion into N-H bonds amines prepare chiral α-amino derivatives with enantioselectivity. Under irradiation visible light, diazo compounds produce high-energy carbenes are captured by form ylide intermediates, and then the newly designed acids, spiro phosphamides, promote proton transfer ylides afford products. Computational kinetic studies uncover principle for rational design proton-transfer explain how accelerate this provide stereocontrol.

Language: Английский

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Visible-Light-Induced Annulation of Iodonium Ylides and 2-Isocyanobiaryls to Access 6-Arylated Phenanthridines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8360 - 8368

Published: June 1, 2023

A 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4-CzIPN)-photocatalyzed cascade arylation/cyclization reaction of 2-isocyanobiaryls and iodonium ylides was established for the synthesis 6-arylated phenanthridines. This is first example employing as aryl radical sources in a visible-light-induced cyclization reaction.

Language: Английский

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