Photoinduced Regioselective Sulfonylsulfination of Alkenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3664 - 3674

Published: Feb. 21, 2024

Regioselective 1,2-dichalcogenation of alkenes has attracted significant attention in modern organic synthetic chemistry. While there are a plethora methods to access alkene dichalcogenated architectures, sulfonylsulfination is extremely challenging due the inherent characteristics sulfur atom. Herein, multicomponent fragment coupling alkenes, sulfinates, and DABSO was developed construct densely functionalized sulfonylsulfinated products, which otherwise access, with broad substrate scope group tolerance under mild operationally simple conditions, using an inexpensive 100–1000 ppm photocatalyst. In addition, protocol applied late-stage functionalization complex molecules, obtained products were converted into diverse downstream transformations demonstrate their potential. Experimental theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl sulfinyl oxygen radical mutual radical–polar crossover coupling. This strategy provides previously inaccessible good-to-high regio- stereoselectivity, along opening up unexplored directions.

Language: Английский

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Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

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Electrochemical difunctionalization of alkenes and alkynes for the synthesis of organochalcogens involving C–S/Se bond formation

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(2), P. 597 - 630

Published: Nov. 23, 2023

This review highlights the recent progress in electrochemical difunctionalization of alkenes and alkynes involving C–S/Se bond formation to access organochalcogen frameworks.

Language: Английский

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An electrocatalytic mono-functionalization of alkenes towards alkenyl selenium sulfonates

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this study, a straightforward and environmentally benign electrochemical mono-functionalization of alkenes has been established for the synthesis alkenyl selenium sulfonates using elemental as source.

Language: Английский

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Electrophotocatalytic Tellurosulfonylation of Alkynes for the Synthesis of β-(Telluro)vinyl Sulfones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6114 - 6119

Published: July 5, 2024

Difunctionalization of alkynes has gained a lot interest in current organic chemistry. Herein, we developed an electrophotocatalytic multicomponent cascade reaction and indoles with sulfinic acid sodium salts using elemental tellurium as the source. Using synergistic anodic oxidation visible-light irradiation, various β-(telluro)vinyl sulfones have been prepared. This strategy features mild conditions, excellent substrate scope, readily available starting materials, great functional group tolerance.

Language: Английский

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Recent advances in selective mono-/dichalcogenation and exclusive dichalcogenation of C(sp²)–H and C(sp³)–H bonds

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 22(4), P. 645 - 681

Published: Dec. 23, 2023

Organochalcogen compounds are prevalent in numerous natural products, pharmaceuticals, agrochemicals, polymers, biological molecules and synthetic intermediates. Direct chalcogenation of C-H bonds has evolved as a step- atom-economical method for the synthesis chalcogen-bearing compounds. Nevertheless, direct severely lags behind C-C, C-N C-O bond formations. Moreover, compared with monochalcogenation, reports selective mono-/dichalcogenation exclusive dichalcogenation relatively scarce. The past decade witnessed significant advancements various C(sp

Language: Английский

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Photoinduced site-selective thiosulfinylation of alkynols for the synthesis of oxathiolene oxides

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110900 - 110900

Published: Jan. 1, 2025

Language: Английский

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Four-Component Radical 1,2-Selenosulfonylation of Allenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5705 - 5712

Published: June 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.

Language: Английский

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Reactions of alkynes with C–S bond formation: recent developments

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(32), P. 6443 - 6484

Published: Jan. 1, 2024

Alkynes are important in organic synthesis. This review mainly focuses on the recent advances (2013–2023) alkynes with C–S bond formation, based more than 30 kinds of sulfur reagents.

Language: Английский

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Iodine(III)-Mediated Photochemical C–H Azolation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9305 - 9310

Published: Oct. 23, 2024

A systematic radical polarity analysis framework is formulated herein for the projection of reactivity patterns. An iodine(III)-mediated photochemical C–H azolation reaction has been envisaged and developed based on set empirical guidelines. The synthesis features an environmentally benign reagent, mild conditions, operationally simple protocol, a broad substrate scope. inclusive demonstration ether, thioether, amide, benzylic, allylic bonds promises wide-ranging synthetic utility.

Language: Английский

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