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

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

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Published inChemical science (Cambridge) Vol. 9; no. 20; pp. 4644 - 4649
Main Authors Volpe, Rohan, Lepage, Romain J., White, Jonathan M., Krenske, Elizabeth H., Flynn, Bernard L.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 2018
Royal Society of Chemistry
Subjects
Aromatic compounds
Chemistry
Chemistry, Multidisciplinary
Ketones
Nucleophiles
Physical Sciences
Science & Technology
Substitutes
Substrates
TORQUOSELECTIVITY
ALKENES
YNAMIDES
CARBON
STEREOSELECTIVE-SYNTHESIS
ZIRCONOCENE DERIVATIVES
ALKYNES
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Summary:Carbometalation of oxazolidinone (Ox)-substituted ynamides is used to generate highly substituted Ox-divinyl (and aryl vinyl) ketones for use in Nazarov cyclizations. The Ox-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 degrees) stereocentres.
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ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc00031j