Asymmetric synthesis of multiple quaternary stereocentre-containing cyclopentyls by oxazolidinone-promoted Nazarov cyclizations

Carbometalation of oxazolidinone ( )-substituted ynamides is used to generate highly substituted -divinyl (and aryl vinyl) ketones for use in Nazarov cyclizations. The -group serves as a remarkably effective chiral activating group, enabling the torquoselective Nazarov cyclization of these stericall...

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Published in:Chemical science (Cambridge) 2018, Vol.9 (20), p.4644-4649
Main Authors: Volpe, Rohan, Lepage, Romain J, White, Jonathan M, Krenske, Elizabeth H, Flynn, Bernard L
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Language:English
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Aromatic compounds
Chemistry
Ketones
Nucleophiles
Substitutes
Substrates
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cited_by cdi_FETCH-LOGICAL-c472t-aa4867d0d49d881a7066fa65894943982e13312d81db936d3b5f89f1372884c33
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description Carbometalation of oxazolidinone ( )-substituted ynamides is used to generate highly substituted -divinyl (and aryl vinyl) ketones for use in Nazarov cyclizations. The -group serves as a remarkably effective chiral activating group, enabling the torquoselective Nazarov cyclization of these sterically congested substrates to be performed under mild conditions. It also serves as a charge-stabilizing group in the intermediate oxyallyl cation, suppressing undesired [1,2]-sigmatropic shifts of neighboring substituents and facilitating the regio- and stereoselective incorporation of nucleophiles to yield cyclopentanoids containing up to three contiguous all-carbon quaternary (4°) stereocentres.
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subjects Aromatic compounds
Chemistry
Ketones
Nucleophiles
Substitutes
Substrates
title Asymmetric synthesis of multiple quaternary stereocentre-containing cyclopentyls by oxazolidinone-promoted Nazarov cyclizations
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