Oxo-rhenium-catalyzed Biomimetic Cyclizations and Late-stage Electrochemical C–H Oxidation of Unactivated C(sp3)–H Bonds

Part A: Oxo-rhenium-catalyzed Biomimetic Cyclization Biomimetic cyclizations are remarkable tools because a significant increase in molecular complexity can be obtained in a single step. In the first part of my PhD, a new method to promote biomimetic cyclizations of terpenoid-like starting materials using an oxo-rhenium complex as a catalyst is described. This proof of concept, if further explored, will give access to useful building blocks that can be employed for the total synthesis of natural products. Part B: Electrochemical C–H Oxidation The site-specific oxidation of “strong”, non-acidic C(sp3)–H bonds is a rewarding, yet difficult topic in organic synthesis. In the second part of my PhD, N-ammonium ylides are described as tunable, electrochemically driven oxidants for site-specific, chemoselective C(sp3)–H oxidation. This ylide-based approach to C–H oxidation exhibits a unique selectivity relative to other classes of chemical oxidants and can be applied to real-world problems.