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

Date
2019
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.
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Description
peer-reviewed
Publisher
American Chemical Society
Citation
Journal of Organic Chemistry;84 (12), pp. 7543-7563
Collections
Chemical Sciences
Bernal Institute
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Keywords
desymmetrization, copper
ULRR Identifiers
https://hdl.handle.net/10344/8912
 https://doi.org/10.34961/14960
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Funding Information
Science Foundation Ireland (SFI), Irish Research Council (IRC)
Sustainable Development Goals
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Type
Article
Rights
https://creativecommons.org/licenses/by-nc-sa/1.0/
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