Supercritical Carbon Dioxide as a Reaction Medium for Silane-Mediated Free-Radical Carbonylation of Alkyl Halides

Kishimoto, Y.; Ikariya, Takao

doi:10.1021/jo001135q

Cited by 29 publications

(8 citation statements)

References 24 publications

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“…We also applied a radical reaction system using Bu 4 NBH 3 CN–AIBN for the corresponding three-component coupling reaction with the incorporation of CO, for which tributyltin hydride or TTMSS was used in the original processes . When a mixture of 1-iodooctane ( 1a ), CO, and methyl acrylate ( 2a′ ) (2 equiv) with Bu 4 NBH 3 CN was subjected to the radical reaction conditions, 1,4-dicarbonyl compound 8aa′ was obtained in 62% yield (Table , entry 1).…”

Section: Resultsmentioning

confidence: 99%

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

et al. 2014

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Cyanoborohydrides are efficient reagents in the reductive addition reactions of alkyl iodides and electron-deficient olefins. In contrast to using tin reagents, the reaction took place chemoselectively at the carbon-iodine bond but not at the carbon-bromine or carbon-chlorine bond. The reaction system was successfully applied to three-component reactions, including radical carbonylation. The rate constant for the hydrogen abstraction of a primary alkyl radical from tetrabutylammonium cyanoborohydride was estimated to be <1 × 10(4) M(-1) s(-1) at 25 °C by a kinetic competition method. This value is 3 orders of magnitude smaller than that of tributyltin hydride.

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Section: Resultsmentioning

confidence: 99%

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

et al. 2014

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“…This clearly demonstrates that the use of a slow mediator ensures that the lifetimes of each intermediate radical are sufficient to permit their participation in consecutive CaC bondforming reactions. A highly sophisticated system for the quantitative synthesis of ketones has also been created using supercritical CO 2 as a reaction medium [24].…”

Section: Multicomponent Coupling Reactions Mediated By Group 14 Radicalsmentioning

confidence: 99%

Free‐Radical‐Mediated Multicomponent Coupling Reactions

Tojino

Ryu

2005

Multicomponent Reactions

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“…Methods for the hydroacylation of alkenes within the context of this work: (a) traditional catalytic hydroacylation of alkenes; (b) alkene hydroacylation via acyl radical intermediates; (c) radical carbonylative alkene hydroacylation; − , (d) this work: carbonylative alkene hydroacylation with alkyl halides.…”

Section: Introductionmentioning

confidence: 99%

“…An important and emergent strategy for the assembly of ketones via acyl radicals is carbonylative alkene hydroacylation (Figure c). − Carbonylative hydroacylation proceeds by the generation of a carbon-centered radical that traps CO to generate the acyl radical species. This multicomponent approach offers improved modularity, and its use of cost-effective and abundant carbon monoxide (CO) as a C1 building block has attracted considerable interest.…”

Section: Introductionmentioning

confidence: 99%

Carbonylative Hydroacylation of Styrenes with Alkyl Halides by Multiphoton Tandem Photoredox Catalysis in Flow

2022

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The abundance, structural diversity, and versatility of ketones give prominence to this carbonyl functional group in synthetic chemistry. The assembly of ketones via the carbonylative hydroacylation of alkenes represents a powerful modular strategy for the synthesis of unsymmetric ketone products. Here, we report the photocatalytic carbonylative hydroacylation of styrenes with unactivated alkyl halides. This protocol unifies the visible-light multiphoton catalytic cycle of [Ir(ppy)2(dtb-bpy)]+ with flow chemistry to engage energy-demanding alkyl bromides and iodides at moderate pressures of carbon monoxide. The mild and practical methodology was employed to prepare a diverse array of 44 unsymmetric dialkyl ketones from primary, secondary, and tertiary unactivated alkyl halides. We demonstrate the application of flow chemistry technology to achieve spatially resolved chemoselectivity and broad functional group tolerance for the mild generation of functionalized C(sp3)-rich ketone products.

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Supercritical Carbon Dioxide as a Reaction Medium for Silane-Mediated Free-Radical Carbonylation of Alkyl Halides

Cited by 29 publications

References 24 publications

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

Free‐Radical‐Mediated Multicomponent Coupling Reactions

Carbonylative Hydroacylation of Styrenes with Alkyl Halides by Multiphoton Tandem Photoredox Catalysis in Flow

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