Transition metal-free synthesis of α-aryl ketones <i>via</i> oxyallyl cation capture with arylboronic acids

Huang, Weian; Huang, Gong‐Bin; Zhu, Weiwei; Weng, Jiang; Lu, Gui

doi:10.1039/d0qo00447b

Cited by 10 publications

(3 citation statements)

References 78 publications

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“…Unless otherwise noted, all reagents and solvents were obtained from commercial sources and, where appropriate, purified prior to use. N-vinyl oxindole nitrones 1a – 1v , 1w–1y, α-tosyloxy ketones 2a – 2i are prepared according to the reported literature.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Yuan,

Wu,

Fang

et al. 2023

J. Org. Chem.

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A variety of spirooxindole-1,2-oxazinan-5-one derivatives were prepared in moderate to excellent yields through 2,2,2-trifluoroethanol (TFE)-promoted [3 + 3] cycloaddition of N-vinyl oxindole nitrones with oxyallyl cations generated from α-tosyloxy ketones under mild reaction conditions. Mechanistic studies revealed that [3 + 3] cycloaddition might involve two possible reaction pathways, including direct [3 + 3] cycloaddition of N-vinyl oxindole ntirones with oxyallyl cations, or the addition of TFE to N-vinyl oxindole nitrones, sequential addition to oxyallyl cations, elimination, and cyclization. The present method features mild reaction conditions, broad substrate scope, good functional group tolerance, easy gram scalable preparation, and new applications of TFE.

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Section: Methodsmentioning

confidence: 99%

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Yuan,

Wu,

Fang

et al. 2023

J. Org. Chem.

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“…Since then, oxyallyl cations generated from α-haloketones and α-tosyloxyketones have been paid attention as a transient electrophilic species and versatile reactive intermediates for the Nazarov cyclization and [ m + 3] cycloadditions . Recently, Chi, MacMillan, and Lu developed a nucleophilic α-substitution of ketones via oxyallyl cations using indoles and arylboronic acids …”

mentioning

confidence: 99%

Preparation of Alkyl Di(p-tolyl)sulfonium Salts and Their Application in Metal-Free C(sp³)–C(sp³) and C(sp³)–C(sp²) Bond Formations

et al. 2023

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Alkyldiarylsulfonium salts were synthesized by a combination of active sulfonium species, prepared through the activation of diarylsulfoxide, and alkyl nucleophiles. The isolated sulfonium salts were subjected to the allylation and cyclopropanation of the active methylene compounds and metal-free C(sp3)–C(sp2) couplings via oxyallyl cation intermediates under mild conditions. The series of reactions included an umpolung strategy for the coupling of alkyl nucleophiles and metal-free C–C bond formation using sulfonium salts.

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“…Oxyallyls are versatile reactive intermediates and have been extensively used as electrophiles , and dipolarophiles − in various reactions. Their synthetic utility is amply demonstrated by the synthesis of natural products. − However, owing to the unique planar structure of oxyallyls for which there is no general means to discriminate between the two faces, catalytic asymmetric reactions involving oxyallyls remain largely unexplored.…”

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confidence: 99%

Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates

et al. 2021

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The unique structure of oxyallyls represents a significant challenge for their catalytic asymmetric applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated in situ from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4(1H)-ones were obtained in up to 98% yields with excellent stereoselectivities (up to 99% ee, > 99:1 dr).

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Transition metal-free synthesis of α-aryl ketones via oxyallyl cation capture with arylboronic acids

Abstract: α-Arylated ketones were accessed via oxyallyl cation capture with arylboronic acids in good yields with broad substrate tolerance.

Cited by 10 publications

References 78 publications

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Preparation of Alkyl Di(p-tolyl)sulfonium Salts and Their Application in Metal-Free C(sp³)–C(sp³) and C(sp³)–C(sp²) Bond Formations

Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates

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Transition metal-free synthesis of α-aryl ketones via oxyallyl cation capture with arylboronic acids

Abstract: α-Arylated ketones were accessed via oxyallyl cation capture with arylboronic acids in good yields with broad substrate tolerance.

Cited by 10 publications

References 78 publications

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Synthesis of Spirooxindole-1,2-oxazinan-5-ones through 2,2,2-Trifluoroethanol Promoted [3 + 3] Cycloaddition of N-Vinyl Oxindole Nitrones and Oxyallyl Cations

Preparation of Alkyl Di(p-tolyl)sulfonium Salts and Their Application in Metal-Free C(sp3)–C(sp3) and C(sp3)–C(sp2) Bond Formations

Catalytic Asymmetric (3 + 3) Cycloaddition of Oxyallyl Zwitterions with α-Diazomethylphosphonates

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Preparation of Alkyl Di(p-tolyl)sulfonium Salts and Their Application in Metal-Free C(sp³)–C(sp³) and C(sp³)–C(sp²) Bond Formations