Vinylation of Iododifluoromethylated Alcohols via a Light-Promoted Intramolecular Atom-Transfer Reaction

Panferova, Liubov I.; Стручкова, Марина И.; Dilman, Alexander D.

doi:10.1055/s-0036-1590855

Cited by 10 publications

(3 citation statements)

References 12 publications

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“…Notably, this redox-neutral mechanism contrasts to the radical chain mechanism suggested by other studies. [19][20] Scheme 5. Proposed mechanism By comparison, subjecting iodide 4a to BEt3 and trace levels of oxygen with 1 H NMR monitoring results in the formation of a cyclized iodide intermediate (17,Scheme 4c).…”

Section: Scheme 4 Mechanistic Investigationsmentioning

confidence: 99%

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Baussière

Haugland

2023

Preprint

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Radical group transfer is a powerful tool for the formation of C–C bonds. These processes typically involve radical addition to C–C π bonds, followed by fragmentation of the cyclic intermediate. Despite the advantageous lability of organosilanes in this context, silicon-tethered radical acceptor groups have remained underexplored in radical group transfer reactions. We report a general photoredox-catalyzed protocol for the radical group transfer of vinyl and alkynyl silanes onto sp3 carbons, using activated and unactivated iodides as radical precursors. Our method displays high diastereoselectivity and excellent functional group tolerance. Mechanistic investigations revealed the key role played by silicon in facilitating a single-electron oxidation step, which leads to direct ring-opening and an overall redox-neutral process.

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Section: Scheme 4 Mechanistic Investigationsmentioning

confidence: 99%

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Baussière

Haugland

2023

Preprint

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“…Alkene group transfer was achieved with electronically activated alkyl iodides using an Ir(III) photocatalyst and irradiation with blue light (Scheme 1c). 19 Similarly, irradiation of an Ir(III) photocatalyst resulted in alkene group transfer of tertiary, activated alkyl bromides (Scheme 1d). 20 Beyond these successful initial demonstrations, a general method for group transfer reactions of silicon-tethered alkenes and alkynes has not yet been reported.…”

Section: ■ Introductionmentioning

confidence: 99%

“…More recently, two examples of radical cyclizations with vinyl silanes initiated by photoredox catalysis have been shown. Alkene group transfer was achieved with electronically activated alkyl iodides using an Ir( iii ) photocatalyst and irradiation with blue light (Scheme c) . Similarly, irradiation of an Ir( iii ) photocatalyst resulted in alkene group transfer of tertiary, activated alkyl bromides (Scheme d) .…”

Section: Introductionmentioning

confidence: 99%

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Baussière

Haugland

2023

J. Org. Chem.

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Radical group transfer is a powerful tool for the formation of C−C bonds. These processes typically involve radical addition to C−C π bonds, followed by fragmentation of the resulting cyclic intermediate. Despite the advantageous lability of organosilanes in this context, silicon-tethered radical acceptor groups have remained underexplored in radical group transfer reactions. We report a general photoredox-catalyzed protocol for the radical group transfer of vinyl and alkynyl silanes onto sp 3 carbons, using activated and unactivated iodides as radical precursors. Our method displays high diastereoselectivity and excellent functional group tolerance, and enables direct formation of group transfer products by in situ ring opening. Mechanistic investigations revealed that the reaction proceeds via an unusual dual catalytic cycle, resulting in an overall redox-neutral process.

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Visible Light Promoted 2‐Bromotetrafluoroethylation of Nitrones

et al. 2018

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A reaction of nitrones with 1,2-dibromotetrafluoroethane affording bromodifluoroethylsubstituted hydroxylamines is described. The process is performed in the presence of a ruthenium photocatalyst and ascorbic acid as a stoichiometric reducing agent and is mediated by blue light irradiation. The fluroalkylation products can undergo chemoselective transformations involving either NÀO or CÀBr bonds furnishing various tetrafluorinated compounds.

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Vinylation of Iododifluoromethylated Alcohols via a Light-Promoted Intramolecular Atom-Transfer Reaction

Cited by 10 publications

References 12 publications

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Radical Group Transfer of Vinyl and Alkynyl Silanes Driven by Photoredox Catalysis

Visible Light Promoted 2‐Bromotetrafluoroethylation of Nitrones

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