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Upstream product

• 1073-67-2 4-vinylbenzyl chloride 
• 211562-21-9 sodium 2,2,6,6-tetramethylpiperidine-1-oxide 
• 2564-83-2 2,2,6,6-tetramethyl-piperidine-N-oxyl 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 

Relevant academic research and scientific papers

Oxoammonium Salt-Mediated Vicinal Oxyazidation of Alkenes with NaN3: Access to β-Aminooxy Azides

An approach to the vicinal oxyazidation of alkenes has been achieved under mild and transition metal-free conditions. This method utilizes NaN3 as the azidation agent and 2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (TEMPO

Photoswitchable Regiodivergent Azidation of Olefins with Sulfonium Iodate(I) Reagent

Photoswitchable strategy for selective azidation of structurally diverse olefins under transition-metal-free conditions is reported. The unprecedented reactivity of trimethylsulfonium [bis(azido)iodate(I)] species under visible light allows radical azidooxygenation of the C═C πbond with distinctive selectivity. In the absence of visible light, the reaction proceeds through an ionic intermediate which led to complementary regioselectivity to provide α-alkyl azides. Mechanistic studies reveal that light-controlled regiodivergent azidation involving radical or an ionic pathway can be accomplished with exclusive regioselectivity.

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

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

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.