Due to burgeoning interest in the pharmaceutical industry in exploiting optically active α-aminoboronic derivatives as bioisosteres of α-amino acid derivatives, the discovery of methods for their catalytic asymmetric synthesis is an important challenge. Herein, we establish that a chiral copper catalyst (generated in situ from commercially available components) can achieve the enantioselective synthesis of α-aminoboronic derivatives via the coupling of two readily available partners, a carbamate and a racemic α-chloroboronate ester. Furthermore, we describe mechanistic studies that played a key role in the development of this new method and that provide insight into the optimized process.