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 lanthanium), as well as Brønsted acids and bases. Catalysts Many metal-ligand combinations have been reported to catalyze hydroamination, including main group elements including alkali metals such as lithium, group 2 metals such as calcium, as well as group 3 metals such as aluminum, indium, and bismuth. In addition to these main group examples, extensive research has been conducted on the transition metals with reports of early, mid, and late metals, as well as first, second, and third row elements. Finally the lanthanides have been thoroughly investigated. Zeolites have also shown utility in hydroamination. Catalytic cycles The mechanism of metal-catalyzed hydroamination has been well studied. Particularly well studied is the organolanthanide catalyzed intramolecular hydroamination of alkenes. First, the catalyst is activated by amide exchange, generating the active catalyst (i). Next, the alkene inserts into the Ln-N bond (ii). Finally, protonolysis occurs generating the cyclized product while also regenerating the active catalyst (iii). Although this mechanism depicts the use of a lanthanide catalyst, it is the basis for rare-earth, actinide, and alkali metal based catalysts. Late transition metal hydroamination catalysts have multiple models based on the regioselective determining step. The four main categories are (1) nucleophilic attack on an alkene alkyne, or allyl ligand and (2) insertion of the alkene into the metal-amide bond. Generic catalytic cycles appear below. Mechanisms are supported by rate studies, isotopic labeling, and trapping of the proposed intermediates. Thermodynamics and kinetics The hydroamination reaction is approximately thermochemically neutral.