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Updated: Mar 25, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Remote functionalization through alkene isomerization
Alexandre Vasseur1, Jeffrey Bruffaerts1, Ilan Marek1
1The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000 Israel.
Abstract:
Exploiting the reactivity of one functional group within a molecule to generate a reaction at a different position is an ongoing challenge in organic synthesis. Effective remote functionalization protocols have the potential to provide access to almost any derivatives but are difficult to achieve. The difficulty is more pronounced for acyclic systems where flexible alkyl chains are present between the initiating functional group and the desired reactive centres. In this Review, we discuss the concept of remote functionalization of alkenes using metal complexes, leading to a selective reaction at a position distal to the initial double bond. We aim to show the vast opportunity provided by this growing field through selected and representative examples. Our aim is to demonstrate that using a double bond as a chemical handle, metal-assisted long-distance activation could be used as a powerful synthetic strategy.
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