Peer-Reviewed Journal Details
Mandatory Fields
Brouder, Thomas A.; Slattery, Catherine N.; Ford, Alan; Khandavilli, U. B. Rao; Skořepov, Elika; Eccles, Kevin S.; Lusi, Matteo; Lawrence, Simon E.; Maguire, Anita R.
2019
Unknown
The Journal of Organic Chemistry
Desymmetrization by Asymmetric Copper-Catalyzed Intramolecular CH Insertion Reactions of a-Diazo--oxosulfones
Published
Optional Fields
Copper-catalyzed Asymmetric
Effective desymmetrization in copper-catalyzed intramolecular CH insertion reactions of a-diazo--oxosulfones in the formation of fused thiopyran dioxides is described for the first time. The use of a copperbis(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 CH insertion on both diastereo- and enantioselectivities of these intramolecular CH 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 CH insertion.
0022-3263
https://pubs.acs.org/doi/10.1021/acs.joc.8b03160
10.1021/acs.joc.8b03160
Grant Details