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Synthesis 2013; 45(15): 2179-2187
DOI: 10.1055/s-0033-1338892
DOI: 10.1055/s-0033-1338892
paper
Alkylation and Ring Opening of Perfluoroalkyl- and Perfluoroaryl-Substituted 2-Siloxycyclopropanecarboxylates Yielding Fluorinated γ-Oxo Esters or β,γ-Unsaturated Ketones
Further Information
Publication History
Received: 10 April 2013
Accepted after revision: 30 April 2013
Publication Date:
17 June 2013 (online)
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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.
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- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
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For reviews on donor–acceptor cyclopropanes, see:
For an interesting theoretical study on donor–acceptor cyclopropanes, see:
For a recent example of fluorinated cyclopropanes, see:
Selected reviews:
For recent original reports, see:
Selected reviews:
For selected publications dealing with in situ generation of carbonyl compounds from d–a cyclopropanes and their direct subsequent functionalization in one-pot procedures, see:
For a mechanistic study, see:
For substitution by organolithium species, see:
For similar reactions of other cyclopropanes see: