Catalytic Diamination and Functionalization of Alkenes

Catalytic diamination and functionalization of alkenes encompasses a suite of methods by which two nitrogen-based substituents or a nitrogen and another functional group are installed across a carbon–carbon double bond. These vicinal diamines and amino-functional products represent privileged motifs in pharmaceuticals, agrochemicals and ligand design. Central challenges in this field include control over regioselectivity and chemoselectivity, compatibility with sensitive functional groups and the ability to use readily available amine sources. A range of strategies has been developed to address these issues, including transition-metal catalysis that accesses high-oxidation-state intermediates, photochemical generation of aminium radicals, electro-oxidative processes and reagent-driven ionic pathways. Recent advances have expanded substrate scope to unactivated alkenes and allenes, introduced mild, oxidant-free protocols and demonstrated continuous-flow scalability. Together, these developments have elevated difunctionalisation techniques to versatile, efficient routes for the preparation of complex diamines and related frameworks with high stereo- and regiocontrol.

Research from Nature Portfolio

Recent studies have demonstrated a modular diamination of allenes to afford beta,gamma-diamino carboxylates and sulfones via an ionic mechanism that employs in situ generated iodoamine species activated by halogen bonding with chloride. This protocol exhibits broad functional-group tolerance and scalability, with experimental and computational insights revealing the energy-lowering role of halogen-bond activation. Parallel work has introduced an electro-oxidative 1,2-amino oxygenation of alkenes that couples commercial oxygen and nitrogen sources in the absence of external oxidants, benefiting from hydrogen evolution for mild, continuous-flow operation and offering a general platform for N-centred radical-mediated functionalisation. Foundational research has also unlocked vicinal diamination under metal-free conditions by double nucleophilic attack on a trifluoropropenyliodonium synthon, enabling selective access to trifluoromethylated ethylene diamines at ambient temperature.

Catalytic Diamination and Functionalization of Alkenes publication trend

The graph below shows the total number of articles in catalytic diamination and functionalization of alkenes across all publications each year (not limited to Nature Index journals).

Technical terms

Alkene: A hydrocarbon containing at least one carbon–carbon double bond.

Diamination: The simultaneous installation of two nitrogen substituents across adjacent carbon atoms of an alkene.

Difunctionalisation: The process of adding two distinct functional groups to a substrate in a single operation.

Electro-oxidative functionalisation: A method that uses electrical current to promote oxidative transformations without stoichiometric chemical oxidants.

N-centred radicals: Reactive species in which the radical character is located on a nitrogen atom, often employed for C–N bond formation.

References

1. Modular and practical diamination of allenes. Nature Communications (2023).
2. 1,2-Amino oxygenation of alkenes with hydrogen evolution reaction. Nature Communications (2022).
3. Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines. Nature Communications (2020).
4. Copper-catalyzed diamination of unactivated alkenes with hydroxylamines. Chemical Science (2015).
5. Photoinduced Olefin Diamination with Alkylamines. Angewandte Chemie International Edition (2020).