Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO-N₃ Charge-Transfer Complex.

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-N₃ into TEMPO^• and azidyl precedes the addition of these radicals across the alkene in the rate-determi

SUBMITTER: Siu JC 

PROVIDER: S-EPMC6212300 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature