A palladium-catalysed enolate alkylation cascade for the formation of adjacent quaternary and tertiary stereocentres
Identifieur interne : 000096 ( Main/Exploration ); précédent : 000095; suivant : 000097A palladium-catalysed enolate alkylation cascade for the formation of adjacent quaternary and tertiary stereocentres
Auteurs : Jan Streuff [États-Unis] ; David E. White [États-Unis] ; Scott C. Virgil [États-Unis] ; Brian M. Stoltz [États-Unis]Source :
- Nature Chemistry [ 1755-4330 ] ; 2010-03.
Abstract
The catalytic enantioselective synthesis of densely functionalized organic molecules that contain all-carbon quaternary stereocentres is a challenge to modern chemical methodology. The catalytically controlled, asymmetric α-alkylation of ketones represents another difficult task and is of major interest to our and other research groups. We report here a palladium-catalysed enantioselective process that addresses both problems simultaneously and allows the installation of vicinal all-carbon quaternary and tertiary stereocentres at the α-carbon of a ketone in a single step. This multiple bond-forming process is carried out on readily available β-ketoester starting materials and proceeds by conjugate addition of a palladium enolate, generated in situ, to activated Michael acceptors. As a result, the CO2 moiety of the substrate is displaced by a C–C fragment in an asymmetric cut-and-paste reaction with high yield, diastereomeric ratio and enantiomeric excess.
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DOI: 10.1038/nchem.518
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The catalytically controlled, asymmetric α-alkylation of ketones represents another difficult task and is of major interest to our and other research groups. We report here a palladium-catalysed enantioselective process that addresses both problems simultaneously and allows the installation of vicinal all-carbon quaternary and tertiary stereocentres at the α-carbon of a ketone in a single step. This multiple bond-forming process is carried out on readily available β-ketoester starting materials and proceeds by conjugate addition of a palladium enolate, generated in situ, to activated Michael acceptors. As a result, the CO2 moiety of the substrate is displaced by a C–C fragment in an asymmetric cut-and-paste reaction with high yield, diastereomeric ratio and enantiomeric excess.</div></front></TEI><affiliations><list><country><li>États-Unis</li></country></list><tree><country name="États-Unis"><noRegion><name sortKey="Streuff, Jan" sort="Streuff, Jan" uniqKey="Streuff J" first="Jan" last="Streuff">Jan Streuff</name></noRegion><name sortKey="Stoltz, Brian M" sort="Stoltz, Brian M" uniqKey="Stoltz B" first="Brian M." last="Stoltz">Brian M. Stoltz</name><name sortKey="Stoltz, Brian M" sort="Stoltz, Brian M" uniqKey="Stoltz B" first="Brian M." last="Stoltz">Brian M. Stoltz</name><name sortKey="Virgil, Scott C" sort="Virgil, Scott C" uniqKey="Virgil S" first="Scott C." last="Virgil">Scott C. Virgil</name><name sortKey="White, David E" sort="White, David E" uniqKey="White D" first="David E." last="White">David E. 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