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Updated: Jul 24, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Catalytic asymmetric defluorinative allylation of silyl enol ethers
Jordi Duran1, Javier Mateos1, Albert Moyano1
1Section of Organic Chemistry, Department of Inorganic and Organic Chemistry, University of Barcelona Carrer Martí i Franquès 1 08028 Barcelona Spain x.companyo@ub.edu https://companyolab.com.
Abstract:
The stereocontrolled installation of alkyl fragments at the alpha position of ketones is a fundamental yet unresolved transformation in organic chemistry. Herein we report a new catalytic methodology able to construct α-allyl ketones via defluorinative allylation of silyl enol ethers in a regio-, diastereo- and enantioselective manner. The protocol leverages the unique features of the fluorine atom to simultaneously act as a leaving group and to activate the fluorophilic nucleophile via a Si-F interaction. A series of spectroscopic, electroanalytic and kinetic experiments demonstrate the crucial interplay of the Si-F interaction for successful reactivity and selectivity. The generality of the transformation is demonstrated by synthesising a wide set of structurally diverse α-allylated ketones bearing two contiguous stereocenters. Remarkably, the catalytic protocol is amenable for the allylation of biologically significant natural products.
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