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 photolysis of organic molecules: the case study of diazo compounds

Chemical Communications, Год журнала: 2023, Номер 59(48), С. 7346 - 7360

Опубликована: Янв. 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.

Язык: Английский

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Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Molecules, Год журнала: 2023, Номер 28(7), С. 3027 - 3027

Опубликована: Март 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Язык: Английский

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Recent advances in the dichalcogenation reactions of unsaturated compounds via double functionalization

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(19), С. 4972 - 5027

Опубликована: Янв. 1, 2023

This review comprehensively summarizes the dichalcogenative functionalization of unsaturated compounds over past decade. The scopes, limitations and detailed reaction mechanisms are also discussed.

Язык: Английский

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Photocatalytic Reactions Involving Diazo Compounds as Radical Precursors

Chinese Journal of Organic Chemistry, Год журнала: 2022, Номер 42(12), С. 4247 - 4247

Опубликована: Янв. 1, 2022

Язык: Английский

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Visible Light-Promoted Radical Reactions of Diazo Compounds

Chinese Journal of Organic Chemistry, Год журнала: 2022, Номер 42(12), С. 3944 - 3944

Опубликована: Янв. 1, 2022

Diazo compounds have rich reactivity and are important synthetic intermediates in organic synthesis.Diazo commonly used as the precursors of transition metal carbenes, relative catalyzed reactions achieved many progresses past decades.In sharp contrast, radical with diazo a key component still less explored.Owing to easy generation diverse under mild conditions, visible-light photoredox catalysis has emerged powerful tool for synthesis.By combination visible light compounds, some novel that different from classical carbene processes been developed, which further extend applications these reagents.The enabled by five years summarized, including:(1) nucluophiles, (2) equivalents carbyne precursors, (3) acceptors, (4) precursors.We wish detailed discussion on mechanism would help audiences understand features realative chemistry.

Язык: Английский

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Radical 1,3-Hydrosulfonylation of Vinyldiazo Compounds with Sulfinyl Sulfones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 4, 2025

Sulfinyl sulfones, as high-valence sulfurization reagents, are widely used to assemble sulfur sources on carbon skeletons, such one-, two-, and four-carbon synthons, access organosulfur compounds. However, their reaction with three-carbon synthons has remained a mystery until now. We report here radical 1,3-hydrosulfonylation of vinyldiazo compounds sulfinyl sulfones. This not only represents the first example sulfones but also opens up application in monofunctionalization.

Язык: Английский

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Four-Component Radical 1,2-Selenosulfonylation of Allenes

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5705 - 5712

Опубликована: Июнь 27, 2024

Selenosulfones, as pivotal pharmaceutical molecule frameworks, have become a research hotspot in modern organic synthesis due to their vital need for efficient preparation. Herein, we developed an iron-catalyzed four-component controllable radical tandem reaction of allenes involving cycloketone oxime esters, 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO), and diphenyl diselenides the complex selenosulfones. This is first case achieving 1,2-selenosulfonylation via process, wherein precise control rates polarity matching enhance high regioselective conversion. The conditions are ecofriendly mild with step-efficiency by forming two new C–S bonds one C–Se bond pot. Moreover, can be achieved replacing esters aryldiazonium tetrafluoroborates this system.

Язык: Английский

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Metal-Free Highly Regioselective 1,4-Sulfonyliodination of 1,3-Enynes

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(4), С. 2034 - 2045

Опубликована: Фев. 7, 2023

Herein, a novel, practical, and green synthetic method using readily available 1,3-enynes with sulfonyl hydrazides I2 through tert-butyl hydroperoxide (TBHP)-mediated 1,4-sulfonyliodination has been developed for synthesizing various tetrasubstituted allenyl iodides under metal-free conditions. Notably, the proposed exhibits broad substrate scope, operational simplicity, tolerance to air, high functional-group tolerance, satisfactory yields, excellent regioselectivity as well involves use of cost-effective reagents such oxidants.

Язык: Английский

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Photocatalytic C(sp³)–H thiolation by a double S_H2 strategy using thiosulfonates

Chemical Communications, Год журнала: 2023, Номер 59(100), С. 14859 - 14862

Опубликована: Янв. 1, 2023

Site-selective thiolation of C(sp 3 )–H bonds was achieved by a double S H 2 strategy, for which thiosulfonates were used as thiolating reagent and decatungstate anion photocatalyst.

Язык: Английский

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