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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Bibliographic Details
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
Format: Article
Language:English
Subjects:
Aromatic compounds
Chemistry
Ketones
Nucleophiles
Substitutes
Substrates
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Summary: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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc00031j