Visible-Light-Promoted Regioselective 1,3-Fluoroallylation of gem-Difluorocyclopropanes
Haidong Liu1, Yi Li1, Ding-Xing Wang1
1Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, People's Republic of China.
Abstract:
A strategically novel protocol for ring-opening functionalization of aryl gem-difluorocyclopropanes (F2CPs), which allows an expedient construction of CF3-containing architectures via visible-light-promoted F-nucleophilic attack manifold, was disclosed. Single electron oxidation of F2CPs was ascribed as the critical step for the success of this transformation by prompting F-nucleophilic attack, as well as the ensuing C-C bond scission. The observed intriguing regioselectivity for fluoroincorporation in this reaction was rationalized by invoking the cation-stabilization property of gem-difluorine substituents and also the thermodynamic gains acquired from forming CF3 functionality. By using cost-effective fluorination reagent and readily available substrates, a broad collection of structurally diversified α-allyl-β-trifluoromethyl ethylbenzene derivatives could be obtained in generally good yields. Further mechanistic investigations proved the engagement of a benzylic radical intermediate in this transformation.
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