Issue 26, 2023

Catalytic asymmetric defluorinative allylation of silyl enol ethers

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.

Graphical abstract: Catalytic asymmetric defluorinative allylation of silyl enol ethers

Supplementary files

Article information

Article type
Edge Article
Submitted
22 mar 2023
Accepted
23 may 2023
First published
24 may 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 7147-7153

Catalytic asymmetric defluorinative allylation of silyl enol ethers

J. Duran, J. Mateos, A. Moyano and X. Companyó, Chem. Sci., 2023, 14, 7147 DOI: 10.1039/D3SC01498C

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