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Published on: June 21, 2017
Ring-Retentive SN2'-Type Alkylation of gem-Dichlorocyclobutenones Enabled by an In Situ Alkene-to-Radical Relay
Zexu Su1, Jianguo Han1, Huifeng Yue1
1Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou350108, China.
Abstract:
A photocatalyst-free radical SN2'-type alkylation of gem-dichlorocyclobutenones with unactivated alkenes is enabled by visible-light-induced C-Zr bond homolysis. Alkylzirconium intermediates generated in situ from terminal or internal alkenes serve as alkyl radical precursors and undergo radical addition/β-fragmentation with gem-dichlorocyclobutenones to afford ring-retained α-chlorocyclobutenones. This protocol avoids preformed radical donors and external photocatalysts, proceeds under mild conditions, tolerates structurally complex substrates, and furnishes multifunctional α-chlorocyclobutenones suitable for further diversification.
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