The development of selective C-N bond forming reactions represents an important research area because amines are prevalent in biologically active natural products, pharmaceuticals, agrochemicals, and ligands. Traditionally, the reactivity and selectivity of amine-forming reactions had a strong dependence on pre-functionalized starting materials which resulted in costly chemical steps. More direct C-H amination or C=C bond aziridination reactions via transition metal-catalyzed nitrene transfer have been brought to the synthetic community's attention recently for their potential to efficiently form valuable C-N bonds. Unfortunately, the development of efficient NT methods has been met with several challenges including substrate-dependent selectivity and the need for costly transition metal catalysts. The work described herein represents a new approach to these reactions in which rationally designed silver catalysts are utilized to achieve high chemo-, regio- and ultimately, enantioselectivity in a catalyst-controlled manner. Chapter 1 serves as an introduction by providing a selected review of literature on recent asymmetric metal-catalyzed nitrene transfer reactions emphasizing the common catalyst design strategies to solve problems associated with selectivity and reactivity. Chapter 2 describes a method for chemo- and enantioselective silver-catalyzed nitrene transfer in which homoallylic carbamates are transformed into [4.1.0]-carbamate-tethered aziridines in good yields and enantiomeric excess (ee) via intramolecular aziridination. The aziridine products undergo nucleophilic ring-opening to yield enantioenriched amines with no erosion in stereochemical integrity. Chapter 3 presents two complementary silver catalysts that are capable of selecting between [Beta] or [gamma] C(sp3)-H bonds residing in similar steric/electronic environments, overriding reaction at a weaker C-H bond in favor of a stronger one, and activating primary C-H bonds. Further experimental and computational studies revealed some mechanistic insights into this system and what seems to be causing this interesting catalyst-controlled regioselectivity. Finally, Chapter 4 offers an extension of the regioselective silver-catalyzed NT, where [gamma]-propargylic-[gamma]-amino alcohol motifs are synthesized with high site- and enantioselectivity. The protocol was enabled by a new optically active bis(oxazoline) ligand designed via a rapid structure-activity relationship analysis.