1449417-69-9Relevant academic research and scientific papers
Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO-N3 Charge-Transfer Complex
Siu, Juno C.,Sauer, Gregory S.,Saha, Ambarneil,MacEy, Reed L.,Fu, Niankai,Chauviré, Timothée,Lancaster, Kyle M.,Lin, Song
, p. 12511 - 12520 (2018)
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-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.
Stereoselective radical azidooxygenation of alkenes
Zhang, Bo,Studer, Armido
, p. 4548 - 4551 (2013/09/24)
Radical azidooxygenation of various alkenes is described. A readily prepared N3-iodine(III) reagent acts as a clean N3-radical precursor. Radical generation is achieved with TEMPONa acting as a mild organic reducing reagent. The C-radical generated after N3-radical addition is efficiently trapped by in situ generated TEMPO. Yields are good to excellent, and for cyclic systems azidooxygenation occurs with excellent diastereoselectivity.
