Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones
| dc.contributor.author | Brouder, Thomas A. | |
| dc.contributor.author | Slattery, Catherine N. | |
| dc.contributor.author | Ford, Alan | |
| dc.contributor.author | Khandavilli, Udaya Bhaskara Rao | |
| dc.contributor.author | Skořepová, Eliška | |
| dc.contributor.author | Eccles, Kevin S. | |
| dc.contributor.author | Lusi, Matteo | |
| dc.contributor.author | Lawrence, Simon E. | |
| dc.contributor.author | Maguire, Anita R. | |
| dc.contributor.funder | Irish Research Council | en |
| dc.contributor.funder | Irish Research Council for Science, Engineering and Technology | en |
| dc.contributor.funder | Science Foundation Ireland | en |
| dc.contributor.funder | European Regional Development Fund | en |
| dc.date.accessioned | 2019-04-29T08:54:36Z | |
| dc.date.available | 2019-04-29T08:54:36Z | |
| dc.date.issued | 2019-03-04 | |
| dc.date.updated | 2019-04-29T08:44:19Z | |
| dc.description.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. | en |
| dc.description.sponsorship | Irish Research Council (GOIPG/2015/3188); | en |
| dc.description.status | Peer reviewed | en |
| dc.description.version | Accepted Version | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.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 | en |
| dc.identifier.doi | 10.1021/acs.joc.8b03160 | en |
| dc.identifier.endpage | 52 | en |
| dc.identifier.issn | 0022-3263 | |
| dc.identifier.journaltitle | The Journal of Organic Chemistry | en |
| dc.identifier.startpage | 1 | en |
| dc.identifier.uri | https://hdl.handle.net/10468/7812 | |
| dc.language.iso | en | en |
| dc.publisher | American Chemical Society, ACS | en |
| dc.relation.project | info:eu-repo/grantAgreement/SFI/SFI Research Centres/12/RC/2275/IE/Synthesis and Solid State Pharmaceutical Centre (SSPC)/ | en |
| dc.relation.project | info:eu-repo/grantAgreement/SFI/SFI Research Infrastructure Programme/15/RI/3221/IE/Process Flow Spectroscopy (ProSpect); Advanced Reaction Understanding using Flow Nuclear Magnetic Resonance (NMR) and Infrared (IR) Spectroscopies, with On-Line Ultra-Performance Liquid Chromatography (UPLC) and Mass Spectrometry (MS)/ | en |
| dc.relation.uri | https://pubs.acs.org/doi/10.1021/acs.joc.8b03160 | |
| dc.rights | 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 | en |
| dc.subject | Copper-catalyzed | en |
| dc.subject | Asymmetric | en |
| dc.subject | C–H insertion | en |
| dc.subject | Copper-mediated desymmetrization | en |
| dc.title | Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones | en |
| dc.type | Article (peer-reviewed) | en |
