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Boryl Radical Mediated Hydro(<i>gem</i>-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes

Ruizeng Zhang, Hao Zhang, Pan Xu, Xuenian Chen, Zhenxing Liu

2024Organic Letters14 citationsDOI

Abstract

NHC boryl radical mediated halogen atom transfer (XAT) is useful in organic synthesis. Yet, most of the reaction ends only with reducing the halogen to hydrogen, that is, the C–X to C–H. This is especially dominant for electron-deficient alkyl halides, where the formed electrophilic radical reacts rapidly with NHC boranes. Herein, by employing a sterically hindered NHC borane as the boryl radical precursor (IPr·BH 3 ), we were able to use the electrophilic-deficient alkyl halide (α-Iodide gem -di(B(pin))methane) in the C–C bond formation reaction. Mono-, disubstituted styrene, aliphatic alkenes, and heteroatom-substituted alkenes were used as reaction partners. Forty hydro( gem -diboryl)methylation products were obtained at room temperature in moderate to good yields. Detailed mechanistic studies revealed that the reaction mainly involved the radical process.

Topics & Concepts

ChemistryBoranesSteric effectsAlkylationMedicinal chemistryAlkeneOrganic chemistryBoronCatalysisOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis
Boryl Radical Mediated Hydro(<i>gem</i>-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes | Litcius