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Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones
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.
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.
Keyword(s): Copper-catalyzed; Asymmetric; C–H insertion; Copper-mediated desymmetrization
Publication Date:
2019
Type: Journal article
Peer-Reviewed: Yes
Language(s): English
Institution: University College Cork
Funder(s): Science Foundation Ireland
Citation(s): 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
Publisher(s): American Chemical Society, ACS
File Format(s): application/pdf
Related Link(s): https://pubs.acs.org/doi/10.1021/acs.joc.8b03160
First Indexed: 2019-04-30 06:30:25 Last Updated: 2019-04-30 06:30:25