Early transition metal-catalyzed C–H alkylation: hydroaminoalkylation for Csp3–Csp3 bond formation in the synthesis of selectively substituted amines

Hydroaminoalkylation is a 100% atom economic method for forming Csp3–Csp3 bonds through C–H activation α to an amine and subsequent reaction with an alkene. When catalyzed by early transition metals{,} this reaction allows for alternative disconnections for the synthesis of structurally complex amines. This method avoids the installation of protecting groups or directing groups and does not require added oxidants{,} or photoredox catalysts. In this feature article{,} we discuss the various selectively substituted amines that can be accessed by hydroaminoalkylation{,} with a special focus on the development of early transition metal catalysts for their rapid{,} step and atom efficient assembly.