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- Title
Enantioselective Desymmetrization of Prochiral Cyclohexanones by Organocatalytic Intramolecular Michael Additions to α,β-Unsaturated Esters.
- Authors
Gammack Yamagata, Adam D.; Datta, Swarup; Jackson, Kelvin E.; Stegbauer, Linus; Paton, Robert S.; Dixon, Darren J.
- Abstract
A new catalytic asymmetric desymmetrization reaction for the synthesis of enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, has been developed. Employing a cyclohexanediamine-derived primary amine organocatalyst, a range of prochiral cyclohexanone derivatives possessing an α,β-unsaturated ester moiety linked to the 4-position afforded the bicyclic products, which possess three stereogenic centers, as single diastereoisomers in high enantioselectivity (83-99 % ee) and in good yields (60-90 %). Calculations revealed that stepwise CC bond formation and proton transfer via a chair-shaped transition state dictate the exclusive endo selectivity and enabled the development of a highly enantioselective primary amine catalyst.
- Subjects
CYCLOHEXANONES; ORGANOCATALYSIS; ESTERS; ALKALOIDS; DIASTEREOISOMERS; TRANSITION state theory (Chemistry)
- Publication
Angewandte Chemie International Edition, 2015, Vol 54, Issue 16, p4899
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201411924