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Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones
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Accepted version
Date
2019-03-04
Authors
Brouder, Thomas A.
Slattery, Catherine N.
Ford, Alan
Khandavilli, Udaya Bhaskara Rao
Skořepová, Eliška
Eccles, Kevin S.
Lusi, Matteo
Lawrence, Simon E.
Maguire, Anita R.
Journal Title
Journal ISSN
Volume Title
Publisher
American Chemical Society, ACS
Published Version
Abstract
Effective desymmetrization in copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones in the formation of fused thiopyran dioxides is described for the first time. The use of a copper–bis(oxazoline)–NaBARF catalyst complex system leads to formation of the major thiopyran dioxide stereoisomer with up to 98:2 dr and up to 98% ee. The effect of varying the bis(oxazoline) ligand, copper salt, and site of C–H insertion on both diastereo- and enantioselectivities of these intramolecular C–H insertion reactions has been investigated. Similarly, desymmetrization in the formation of a fused cyclopentanone proceeds with up to 64% ee. These results represent the highest enantioselectivity reported to date in a copper-mediated desymmetrization through C–H insertion.
Description
Keywords
Copper-catalyzed , Asymmetric , C–H insertion , Copper-mediated desymmetrization
Citation
Brouder, T. A., Slattery, C. N., Ford, A., Khandavilli, U. B. R., Skořepová, E., Eccles, K. S., Lusi, M., Lawrence, S. E. and Maguire, A. R. (2019) 'Desymmetrization by Asymmetric Copper-Catalyzed Intramolecular C–H Insertion Reactions of α-Diazo-β-oxosulfones', The Journal of Organic Chemistry, In Press. doi: 10.1021/acs.joc.8b03160
Copyright
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.joc.8b03160