Oxidative amination of unactivated alkenes via nitrogen atom insertion into carbon-carbon double bonds

The synthesis of nitrogen-containing molecules through C–N bond formation is critical for the discovery and preparation of medicines, agrochemicals and materials. Traditional synthetic methods using alkenes as ubiquitous substrates leverage the reactivity of the C(sp2)–C(sp2) π bond for C–N bond formation. In contrast, methods that can form C–N bonds through complete cleavage of the double bond are scarce, despite the considerable synthetic potential of such a strategy. Here, we report the direct insertion of a nitrogen atom into unactivated carbon-carbon double bonds to access aza-allenium intermediates which can be converted either into nitriles or amidine products, depending on the initial alkene substitution pattern. This operationally simple and highly functional group tolerant reaction works on a wide range of unactivated alkenes. Our mechanistic proposal is supported by chemical trapping experiments, which concomitantly demonstrate the utility of our method to access valuable N-heterocycles. Overall, this study demonstrates the possibility to access reactive nitrogen-containing intermediates (i.e. aza-alleniums), which have ample potential for downstream diversification, from unactivated alkenes, opening new avenues for the discovery and preparation of important products.