Although our electro-chemical protocol 13 circumvents the use of strong chemical oxidants, the need for a metal catalyst and a Brønsted acid (HOAc) as the sacrificial oxidant remains undesirable from a safety perspective. These reactive species often lead to environmentally deleterious wastes and present an explosion hazard when used alongside N 3 −.
![jc sauer model 1913 jc sauer model 1913](http://www.deactivated-guns.co.uk/images/uploads/1913SA/1SAU13-027962_6.jpg)
19 Nevertheless, all methods reported to date require the use of a transition metal or a chemical oxidant, or both. These reactions provide 1,2-diazides in a single step from common alkenes, giving access to vicinally dinitrogenated structures that are highly prevalent in biomedically and synthetically relevant molecules. 13 This work was built on foundational contributions by Minisci, 14 Magnus, 15 Snider, 16 Xu, 17 and others 18 in alkene diazidation using conventional chemical methods. We previously reported a first-generation electrochemical protocol for the diazidation of alkenes catalyzed by Mn ( Scheme 1A, eq 1). In this report, we expand the scope of N-oxyl catalysis in the development of metal-free electrochemical diazidation of alkenes. 12 In these transformations, the persistent radical is used primarily in two capacities: as a single/two-electron oxidant or an H atom abstractor. 7 To date, reactions catalyzed by N-oxyls are largely confined to oxidations of alcohols, 8 aldehydes, 9 amines, 10 (thio)amides, 11 and peroxyl radicals. 5, 6 Nevertheless, the systematic use of the “metallic” character of N-oxyls in catalyst development remains meager. In this fashion, TEMPO has been shown to enable single-electron oxidation events in an inner-sphere manner via the formation of metastable closed-shell intermediates. 4 This feature distinguishes these radicals from common organic compounds and likens them to many transition metal complexes. TEMPO and related N-oxyl radicals can undergo one-electron redox processes, granting access to three discrete oxidation states.
![jc sauer model 1913 jc sauer model 1913](https://www.gunsamerica.com/UserImages/4239/986501450/wm_6289813.jpg)
2 For example, persistent aminoxyl radicals have been extensively explored in catalytic oxidation reactions with both conventional chemical 3 and electrochemical techniques, 4 which has given rise to synthetically useful processes for small-molecule and polymer syntheses.ĭespite significant advances, we contend that the scope of TEMPO chemistry remains to be fully explored. 1 In this context, design and implementation of new catalytic strategies have both expanded the toolbox available for accessing new synthetic targets and transformed the fundamental understanding of reactions involving open-shell pathways.
![jc sauer model 1913 jc sauer model 1913](https://i.ytimg.com/vi/5ucAdfDKBeY/mqdefault.jpg)
The discovery of reactions mediated by organic radicals continues to provide solutions to challenging synthetic problems in traditional two-electron chemistry.