Complex chemical systems often exhibit unpredictable reactivity, which can only be understood through empirical investigation. In this talk, I will present two cases where chemical complexity emerged in total synthesis and catalysis. First, I will describe the asymmetric synthesis of the fungal metabolite collybolide, previously thought to be a kappa opioid receptor (KOR) agonist. Our synthesis overcame significant challenges related to oxidation and scaffold rearrangement, ultimately yielding both enantiomers of collybolide for reevaluation of its biological activity. Second, I will detail the development of an enantioselective, catalytic method for synthesizing Si-stereogenic silyl ethers via a dynamic resolution of chlorosilanes, enabled by the discovery of a novel organocatalyst. This new approach provides access to stereogenic-at-silicon silyl ethers, which hold untapped potential in organic synthesis, pharmaceuticals and materials. These examples highlight how encountering unexpected chemical reactivity can open new pathways for discovery in catalysis and synthesis