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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Synthesis and applications of thiosulfonates and selenosulfonates as free-radical reagents

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 34(4), P. 107736 - 107736

Published: Aug. 11, 2022

Language: Английский

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Visible-Light-Promoted Selective Sulfonylation and Selenylation of Dienes to Access Sulfonyl-/Seleno-benzazepine Derivatives

Organic Letters, Journal Year: 2023, Volume and Issue: 25(22), P. 4208 - 4213

Published: May 30, 2023

A novel visible-light-promoted selective sulfonylation and selenylation of dienes with selenosulfonates has been developed. This technology provides mild access to a wide range sulfonyl benzo[b]azepinones seleno-benzo[b]azepines. Preliminary mechanistic studies suggest that the involves radical engaged cascade process, is accomplished through sequential oxidation/electrophilic cyclization process. The large-scale operation late-stage modification experiment reveal promising utility this protocol.

Language: Английский

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Visible photons as ideal reagents for the activation of coloured organic compounds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Language: Английский

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“Green Is the Color”: An Update on Ecofriendly Aspects of Organoselenium Chemistry

Molecules, Journal Year: 2022, Volume and Issue: 27(5), P. 1597 - 1597

Published: Feb. 28, 2022

Organoselenium compounds have been successfully applied in biological, medicinal and material sciences, as well a powerful tool for modern organic synthesis, attracting the attention of scientific community. This great success is mainly due to breaking paradigm demonstrated by innumerous works, that selenium were toxic would potential impact on environment. In this update review, we highlight relevance these several fields research possibility synthesize them through more environmentally sustainable methodologies, involving catalytic processes, flow chemistry, electrosynthesis, use alternative energy sources, including mechanochemical, photochemistry, sonochemical microwave irradiation.

Language: Английский

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Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles

Advanced Science, Journal Year: 2023, Volume and Issue: 11(3)

Published: Nov. 29, 2023

Abstract Vinyldiazo compounds are one of the most important synthons in construction a cyclic ring. Most photochemical transformations vinyldiazo mainly focusing on utilization their C═C bond site, while reactions taking place at terminal nitrogen atom largely unexplored. Herein, photocatalytic cascade radical cyclization LBRs with reagents through sequential B─N/C─N formation is described. The reaction starts addition (Lewis base–boryl radicals) diazo followed by intramolecular to access wide range boron‐handled pyrazoles good excellent yields. Control experiments, together detailed mechanism studies well explain observed reactivity. Further demonstrate utility this approach for applications pharmaceutical and agrochemical research.

Language: Английский

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Visible-Light-Driven Unsymmetric gem-Difunctionalization of Vinyl Azides with Thiosulfonates or Selenosulfonates

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1683 - 1687

Published: Feb. 16, 2024

Thiosulfonylation and selenosulfonylation of vinyl azides with thiosulfonates selenosulfonates were achieved using Cu(dap)2Cl as a photosensitizer under visible-light irradiation. This reaction is the application azide substrate in group transfer radical addition (GTRA) reaction, through β-difunctionalization, to obtain variety unsymmetric difunctionalized N-unprotected enamines.

Language: Английский

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Visible‐Light‐Induced Photoredox 1,1‐Dichloromethylation of Alkenes with Chloroform

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(9), P. 1573 - 1579

Published: March 31, 2022

Abstract A photoredox 1,1‐dichloromethylation of alkenes with the readily available bulk chemical chloroform was described, furnishing a variety 1,1‐dichloroalkane products selectively. Furthermore, this transformation could proceed smoothly on gram‐scale, and obtained transform into diverse γ‐lactam derivatives simple treatment. Mechanistically, single electron transfer (SET) excited photocatalyst subsequent deprotonation triethylamine generates key α‐aminoradical intermediate, which enables selective Cl‐atom chloroform. The specific selectivity, broad substrate scope, as well mild reaction conditions make strategy especially attractive. magnified image

Language: Английский

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Synthesis of Tetrasubstituted Allenes via Visible-Light-Promoted Radical 1,3-Difunctionalization of Alkynyl Diazo Compounds

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 3976 - 3981

Published: May 27, 2022

Herein, we described an unprecedented process for generating allenyl radicals through radical addition to alkynyl diazo compounds followed by a 1,2-radical shift with the loss of nitrogen. Using this protocol, 1,3-difunctionalization synthesis tetrasubstituted allenes RSO2X (X = SeR', SR', and I) as sources was developed. The reactions were promoted visible light without photocatalyst any additives.

Language: Английский

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Photoredox‐Enabled Self‐(3+2) Cyclization of Vinyldiazo Reagents: Synthesis of Cyclopentenyl α‐Diazo Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 31, 2023

A photocatalytic self-(3+2) cycloaddition of vinyldiazo compounds is described, which provides cyclopentene derivatives with conservation one diazo functional group. Experimental insights and density theory indicate that the reaction triggered by an unusual single electron oxidation compounds, while photolysis for generation free carbene species not involved. The synthetic applications resulting cyclopentenyl α-diazo were demonstrated based on rich chemistry

Language: Английский

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