Abstract
Ortholithiation and reaction with (-)-menthyl p-toluenesulfinate introduces a sulfoxide substituent ortho to the stereogenic Ar-CO axis of an aromatic amide. The sulfoxide exerts a powerful conformational bias on the axis, such that after rapid equilibration at ambient temperature essentially only one of two diastereoisomeric Ar-CO atropisomers is populated. Sulfoxide-lithium exchange by treatment with t-BuLi regenerates the ortholithiated amide in an enantiomerically pure and conformationally stable form. Rapid electrophilic trapping of the organolithium therefore generates highly enantiomerically enriched atropisomeric tertiary aromatic amides. The overall process, involving temporary substitution of lithium to sulfoxide to lithium, amounts to a dynamic resolution under thermodynamic control. Copyright © 2002 American Chemical Society.
Original language | English |
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Pages (from-to) | 5266-5267 |
Number of pages | 1 |
Journal | Journal of the American Chemical Society |
Volume | 124 |
Issue number | 19 |
DOIs | |
Publication status | Published - 15 May 2002 |
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CCDC 187714: Experimental Crystal Structure Determination
Clayden, J. (Contributor), Mitjans, D. (Contributor) & Youssef, L. H. (Contributor), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc69b93, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc69b93&sid=DataCite
Dataset
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CCDC 187715: Experimental Crystal Structure Determination
Clayden, J. (Contributor), Mitjans, D. (Contributor) & Youssef, L. H. (Contributor), Cambridge Crystallographic Data Centre, 2002
DOI: 10.5517/cc69bb4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc69bb4&sid=DataCite
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