Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones

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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.
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American Chemical Society, ACS
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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.
Copper-catalyzed , Asymmetric , C–H insertion , Copper-mediated desymmetrization
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
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