Homoleptic Lanthanide Amide Catalysts for Organic Synthesis: Experiment and Theory

Homoleptic lanthanide trisamides provide a simple and highly accessible bridge between organolanthanide chemistry and the synthetic methodology community, and although they have proven to be competent catalysts in a wide variety of unique transformations, their reactivity, scope, and mechanism remain understudied relative to lanthanide metallocenes and related organometallic catalysts. In this Perspective, we provide a critical review of the recent advances in homoleptic lanthanide-mediated catalysis as they apply to atom-efficient and environmentally benign organic syntheses. Instead of an exhaustive review, we focus on selected examples of the unexpected reactivity displayed by readily available Ln[N(SiMe3)2]3 complexes. By focusing on both the experimental as well as theoretical and mechanistic aspects of this work, we seek to highlight the value, versatility, and underlying concepts governing the unusual catalytic properties of homoleptic lanthanide amides and offer a general outlook on the prospects for this field.