Sulfenate anions (RSO⁻), the conjugate base of sulfenic acids, can serve as versatile organocatalysts for developing new, sustainable methods of bond formation. They possess unique reactivity by combining good nucleophilicity with the ability to act as effective leaving groups. This dual character enables catalytic turnover, with sulfur undergoing changes in oxidation state in the catalytic cycle. Building upon prior work of sulfenate anion catalyzed transformations, including the synthesis of trans-stilbene, stilbene-based polymers, diaryl alkynes, and the diastereoselective synthesis of aziridines, this dissertation expands the utility of sulfenate chemistry into two key areas: chiral sulfenate anion catalyzed enantioselective and diastereoselective aziridination and C-C bond formation via the catalytic Matteson reaction.In Chapter 1, we report a novel organocatalytic approach using enantioenriched [2.2]paracyclophane (PCP) based sulfenate anion catalysts, enabling the synthesis of 18 cyclopropyl-containing aziridines from unactivated imines and commercially available benzyl chlorides in 50%–99% yields with 73%–99% ee and >20:1 dr. This approach fills a gap in the existing methods for aziridine synthesis, facilitating the generation of cyclopropyl-substituted aziridines with high stereoselectivity under mild and transition metal-free reaction conditions. In Chapter 2, we report a catalytic Matteson reaction employing sulfenate anions, enabling C–C bond formation under mild conditions and affording 35 alcohols in 49–98% yields. This transition-metal-free approach eliminates the need for stoichiometric, air-sensitive, pre-formed organometallic reagents and cryogenic temperatures, improving efficiency and addressing scalability challenges. This method serves as a complementary strategy to existing Matteson homologations, providing new approaches to C–C bond formation. Together, these two studies further expand sulfenate anion organocatalysis as a general and powerful tool in organic synthesis.