Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes
- In the oxidative system (t-BuOCl+NaI) trifluoromethanesulfonamide is regio- and stereoselectively added to only one double bond of cyclopentadiene and 1,3-cyclohexadiene giving rise to 1,1,1-trifluoro-N-(5-iodocyclopent-2-en-1-yl)methanesulfonamide 7 and trans-N,N'-cyclohex-3-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 8. The structure of 7 and 8 was determined by X-ray, NMR, and MS. With 1,4-cyclohexadiene, addition to both double bonds occurs with the formation of N,N'-(4-chloro-5-iodocyclohexan-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide) 9. Under the action of sodium iodide in acetone, the latter product undergoes halogenophilic attack with the reduction of the CHI group and elimination of HCl to give trans-N,N'-cyclohex-4-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 10, whose structure was also determined by X-ray analysis. 1,3,5-Cycloheptatriene under these conditions is oxidized to benzaldehyde and does not react with trifluoromethanesulfonamide.
Author details: | Mikhail Yu Moskalik, Bagrat A. Shainyan, Vera V. Astakhova, Uwe SchildeORCiDGND |
---|---|
DOI: | https://doi.org/10.1016/j.tet.2012.10.099 |
ISSN: | 0040-4020 |
Title of parent work (English): | Tetrahedron |
Publisher: | Elsevier |
Place of publishing: | Oxford |
Publication type: | Article |
Language: | English |
Year of first publication: | 2013 |
Publication year: | 2013 |
Release date: | 2017/03/26 |
Tag: | 1,2-Disulfonamides; Allylamides; Cyclodienes; Trifluoromethanesulfonamide; X-ray |
Volume: | 69 |
Issue: | 2 |
Number of pages: | 7 |
First page: | 705 |
Last Page: | 711 |
Funding institution: | Russian Foundation for Basic Research; Deutsche Forschungsgemeinschaft [RFBR 10-03-00110, 12-03-31295, RFBR-DFG 11-03-91334] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |