Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters
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 deriva...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Wiley
2015
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| _version_ | 1826277328422961152 |
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| author | Gammack Yamagata, A Datta, S Jackson, K Stegbauer, L Paton, R Dixon, D |
| author_facet | Gammack Yamagata, A Datta, S Jackson, K Stegbauer, L Paton, R Dixon, D |
| author_sort | Gammack Yamagata, A |
| collection | OXFORD |
| description | 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 C-C 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. |
| first_indexed | 2024-03-06T23:27:15Z |
| format | Journal article |
| id | oxford-uuid:6aca3459-892a-48ea-ab86-d2128a6f112b |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:27:15Z |
| publishDate | 2015 |
| publisher | Wiley |
| record_format | dspace |
| spelling | oxford-uuid:6aca3459-892a-48ea-ab86-d2128a6f112b2022-03-26T18:59:45ZEnantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated estersJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:6aca3459-892a-48ea-ab86-d2128a6f112bEnglishSymplectic Elements at OxfordWiley2015Gammack Yamagata, ADatta, SJackson, KStegbauer, LPaton, RDixon, DA 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 C-C 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. |
| spellingShingle | Gammack Yamagata, A Datta, S Jackson, K Stegbauer, L Paton, R Dixon, D Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title | Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title_full | Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title_fullStr | Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title_full_unstemmed | Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title_short | Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters |
| title_sort | enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular michael additions to α β unsaturated esters |
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