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Published on: May 21, 2019
Photoredox-Catalyzed Defluorinative [4 + 2] Cycloaddition of α-Fluoro-β-keto Esters and Alkynes by Single
Rui-Xue Liu1, Xiu-Long Yang1, Hao-Yuan Li2,3
1Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, State Key Laboratory of New Pharmaceutical Preparations and Excipients, Hebei Research Center of the Basic Discipline of Synthetic Chemistry, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry and Materials Science, Hebei University, Baoding 071002, P. R. China.
Abstract:
A protocol for C-F bond activation using a single organic photocatalyst was developed. The mechanism involves the self-sorting of α-fluorinated-β-keto esters to generate two radicals: one is highly electrophilic and undergoes rapid benzannulation with alkynes to form a series of 1-naphthols; the other is a tertiary carbon radical that serves as a HAT reagent to achieve substrate regeneration. Notably, the released F- acts as an endogenous base in the reaction, obviating the need for external additives.
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