Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles **
Abstract: Efficient protocols for accessing iodo‐substituted diaryl and aryl (vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition‐metal‐free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S‐diarylation, enabling the regioselective late‐stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S‐difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive‐free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl (vinyl) sulfides. A one‐pot strategy combining transition‐metal‐free diarylation and subsequent reduction provided facile access to electron‐rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles ** ; day:13 ; month:01 ; year:2023 ; extent:9
Angewandte Chemie / International edition. International edition ; (13.01.2023) (gesamt 9)
- Creator
- DOI
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10.1002/anie.202216296
- URN
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urn:nbn:de:101:1-2023011414122274414191
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:38 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Mondal, Shobhan
- Di Tommaso, Ester Maria
- Olofsson, Berit
Other Objects (12)
Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles **
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Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert ‐Butoxide
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Reactivity of oxygen and sulfur nucleophiles and basicity scales toward heteroatom Lewis acids
Transition-metal and metal-free activation of organic molecules
Transition‐Metal‐Free Reductive Hydroxymethylation of Isoquinolines
Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles **
Transition‐Metal‐Free Coupling of Polyfluorinated Arenes and Functionalized, Masked Aryl Nucleophiles
Transition metal catalyzed coupling of nitrogen nucleophiles with allenes
Reactions of p-Benzoquinone with Sulfur Nucleophiles
Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert ‐Butoxide
Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert ‐Butoxide
Sulfur-Based Ylides in Transition-Metal-Catalysed Processes
Transition‐Metal‐Free Cleavage of CO
Reactivity of oxygen and sulfur nucleophiles and basicity scales toward heteroatom Lewis acids
Transition-metal and metal-free activation of organic molecules
Transition‐Metal‐Free Reductive Hydroxymethylation of Isoquinolines
Transition‐Metal‐Free Difunctionalization of Sulfur Nucleophiles **
Transition‐Metal‐Free Coupling of Polyfluorinated Arenes and Functionalized, Masked Aryl Nucleophiles
Transition metal catalyzed coupling of nitrogen nucleophiles with allenes
Reactions of p-Benzoquinone with Sulfur Nucleophiles
Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert ‐Butoxide
Hydroalkylation of Vinylarenes by Transition‐Metal‐Free In Situ Generation of Benzylic Nucleophiles Using Tetramethyldisiloxane and Potassium tert ‐Butoxide
Sulfur-Based Ylides in Transition-Metal-Catalysed Processes
Transition‐Metal‐Free Cleavage of CO
Reactivity of oxygen and sulfur nucleophiles and basicity scales toward heteroatom Lewis acids
Transition-metal and metal-free activation of organic molecules