Directed Magnesiation of Polyhaloaromatics using the Tetramethylpiperidylmagnesium Reagents TMP 2 Mg⋅2 LiCl and TMPMgCl⋅LiCl

A convenient and efficient functionalization of polyhaloaromatics via regioselective magnesiation has been developed. Starting from simple, inexpensive but structurally challenging arenes, metallation by magnesium amide bases was achieved under mild conditions. The desired Grignard reagents were sta...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2013-05, Vol.355 (8), p.1553-1560
Main Authors: Unsinn, Andreas, Rohbogner, Christoph J., Knochel, Paul
Format: Article
Language:English
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Summary:A convenient and efficient functionalization of polyhaloaromatics via regioselective magnesiation has been developed. Starting from simple, inexpensive but structurally challenging arenes, metallation by magnesium amide bases was achieved under mild conditions. The desired Grignard reagents were stable towards aryne formation, were obtained in good yields within short reaction times and could be reacted with a variety of typical electrophiles, providing attractive, functionalized building blocks in good to excellent yields. As an application we have prepared the antimicrobial natural product 2,6‐dichloro‐3‐phenethylphenol isolated from the New Zealand liverwort Riccardia marginata . This synthesis involves a mixed bimetallic compound prepared via metallation of a phenylboronic acid pinacol ester derivative and subsequent selective cross‐coupling.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201300185