There is a growing need in organic synthesis for efficient methodologies for the asymmetric synthesis of quaternary carbon centres. One of the most attractive and straightforward methods focuses on the use of asymmetric catalysis for the addition of various types of nucleophiles on prochiral ketones and ketimines. A view of the literature from this growing area of research will be presented in this review, with an emphasis on the pioneer works and milestones brought by the main players in this field.

The catalysed enantioselective formation of carbon–nitrogen bonds by the hydroamination reaction is reviewed. All examples deal with substrates containing non-activated carbon–carbon multiple bonds which are transformed either via intramolecular or intermolecular reactions. Structurally different complexes already provided nitrogen containing compounds/heterocycles with high enantioselectivities.

This Perspective article outlines some of the recent advancements in the development of (chiral) metal-free and late transition metal catalysts for hydroamination of unactivated alkenes.