Hydroamination reactions are atom-efficient processes that generally use readily available and cheap starting materials, therefore a general catalytic strategy is highly desirable. Also, direct catalytic hydroamination strategies have in principle significant benefits over more classical methods to prepare amine containing compounds, including the reduction in the number of synthetic steps required.
However, hydroamination reactions pose some tough challenges for catalysis: Strong electron repulsion of the nitrogen atom lone pair and the electron rich carbon-carbon multiple bond, coupled with hydroamination reactions being entropically disfavoured (particularly the intermolecular version), results in a large reaction barrier. Regioselectivity issues also hamper the synthetic utility of the resulting products, with Markovnikov addition of the amine being the most common outcome over the less favoured anti-Markovnikov addition (see figure). As a result, there are now numerous catalysts that can be utilised in the hydroamination of alkene, allene and alkyne substrates, including various metal based heterogeneous catalysts, early-transition metal complexes (e.g. titanium and zirconium), late-transition metal complexes (e.g. ruthenium and palladium), lanthanide and actinide complexes (e.g. samarium and lanthanum), as well as Brønsted acids and bases.