The net addition of an N-H group across a carbon–carbon double bond represents an extremely efficient method to access amines. In particular, the ability to conduct this transformation in a general and enantioselective manner is quite attractive. In this lecture, we will describe our success in developing a highly regio- and enantioselective process for the hydroamination of a wide range of olefinic substrates. We will also detail our studies in reaction optimization achieved by way of mechanistic studies.