Nucleophilic Fluoroalkylation of α,β-Enones, Arynes, and Activated Alkynes with Fluorinated Sulfones: Probing the Hard/Soft Nature of Fluorinated Carbanions
作者： Chuanfa Ni , Laijun Zhang , Jinbo Hu
DOI: 10.1021/JO702479Z
关键词: Cascade reaction 、 Carbanion 、 Nucleophile 、 Aryne 、 Medicinal chemistry 、 Organic chemistry 、 Chemistry 、 Alkylation 、 Enone 、 Alkyne 、 Regioselectivity
摘要: We have successfully accomplished the nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones. It was found that for acylic although reaction medium structure enones can all influence regioselectivity alkylation reactions, hard/soft nature carbanions played a major role. By using 1,4- 1,2-addition product ratio as probe to determine above-mentioned four halogenated carbanions, order softness these be given follows: [(PhSO2)2CF−] (20) ≈ PhSO2CCl2− (32) > PhSO2CHF− (31) PhSO2CF2− (30). In case aryne (35 precursor) α,β-acetylenic ketones 46 fluorobis(phenylsulfonyl)methane (21), fluorobis(phenylsulfonyl)methylated arenes 36 β-fluorobis(phenylsulfonyl)methylated α,β-enones 47 were obtained corresponding products in good yields. During between 2-fluoro-2-(phenylsul...
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