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Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO–N3Charge-Transfer Complex
- Source :
- Journal of the American Chemical Society; October 2018, Vol. 140 Issue: 39 p12511-12520, 10p
- Publication Year :
- 2018
-
Abstract
- We report a mild and efficient electrochemical protocol to access a variety of vicinally C–O and C–N difunctionalized compounds from simple alkenes. Detailed mechanistic studies revealed a distinct reaction pathway from those previously reported for TEMPO-mediated reactions. In this mechanism, electrochemically generated oxoammonium ion facilitates the formation of azidyl radical via a charge-transfer complex with azide, TEMPO–N3. DFT calculations together with spectroscopic characterization provided a tentative structural assignment of this charge-transfer complex. Kinetic and kinetic isotopic effect studies revealed that reversible dissociation of TEMPO–N3into TEMPO•and azidyl precedes the addition of these radicals across the alkene in the rate-determining step. The resulting azidooxygenated product could then be easily manipulated for further synthetic elaborations. The discovery of this new reaction pathway mediated by the TEMPO+/TEMPO•redox couple may expand the scope of aminoxyl radical chemistry in synthetic contexts.
Details
- Language :
- English
- ISSN :
- 00027863 and 15205126
- Volume :
- 140
- Issue :
- 39
- Database :
- Supplemental Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Periodical
- Accession number :
- ejs46414246
- Full Text :
- https://doi.org/10.1021/jacs.8b06744