Alkylation and Ring Opening of Perfluoroalkyl- and Perfluoroaryl-Substituted 2-Siloxycyclopropanecarboxylates Yielding Fluorinated γ-Oxo Esters or β,γ-Unsaturated Ketones

Abstract

Deprotonation of perfluoroalkyl- and perfluorophenyl-substituted methyl 2-siloxycyclopropanecarboxylates and subsequent reaction with alkyl halides furnished C-1 alkylated cyclopropanes with high diastereoselectivities. Smooth triethylamine trishydrofluoride mediated desilylation and ring opening afforded the corresponding γ-oxo esters in good to excellent yields. Treatment of methyl 2-siloxycyclopropanecarboxylates with Grignard reagents and subsequent ring opening in the presence of acid provided β,γ-unsaturated ketones with fluorine-containing substituents.

Key words

donor–acceptor cyclopropanes - fluorine - γ-oxo esters - ring opening - defluorination

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