The aim of my Ph.D. thesis is to summarize my research on the development of ring-opening polymerization (ROP) of O-carboxyanhydrides (OCAs) to synthesize functionalized, degradable polyesters. Biodegradable polyesters are promising alternatives to conventional petroleum-based non-degradable polyolefins and they are widely used in everyday applications ranging from clothing and packaging to agriculture and biomedicine. Commercially available polyesters, such as poly(lactic-co-glycolic acid), poly(lactic acid), and polycaprolactone, hydrolyze in physicochemical media. They have been approved by FDA and widely used for medical applications. However, the lack of side-chain functionality in polyesters and in corresponding monomers greatly plagues their utility for applications that demand physicochemical properties such as high stiffness, tensile strength and elasticity. Increasing efforts have been devoted to the introduction of pendant groups along the polymer chain in order to modify and modulate the physicochemical properties of polyesters and thereby to expand their applications. Over the last decade, OCAs have emerged as an alternative class of highly active monomers for polyester polymerization. OCAs are prepared from amino acids and thus have a richer range of side chain functionalities than lactone or lactide. Like lactones, OCAs can undergo ROP to obtain polyesters. Unfortunately, current ROP methods, especially those involving organocatalysts, result in uncontrolled polymerization including epimerization for OCAs bearing electron-withdrawing groups, unpredictable molecular weights (MWs), or slow polymerization kinetics. Based on our recent success of Ni/Ir photoredox catalysis allowing for rapid synthesis of high-MWs polyesters, we further explore new polymerization chemistry to use earth-abundant metal complexes to replace expensive rare-earth metal photocatalysts, and practice the polymerization in moderate and energy-efficient reaction conditions. This thesis introduces novel photoredox and electrochemical earth-abundant metal catalysts that overcome above difficulties in the ROP chemistry of OCAs, and allow for the preparation of stereoregular polyesters bearing abundant side-chain functionalities in a highly controlled manner. Specifically, various highly active metal complexes have been developed for stereoselective ROP of OCAs, either using light or electricity, to synthesize syndiotactic or stereoblock copolymers with different thermal properties. Additionally, simple purification protocols of OCAs have also been initially studied, which potentially paves the way to bulk production of functional monomers. In this thesis, I first describe newly-developed photoredox Co/Zn catalysts to achieve a controlled ROP of enantiopure OCAs under mild reaction conditions (Chapter 2). Such discovery is extended to the combination use of Co catalysts with various Zn/Hf complexes that enable stereoselective controlled ROP of racemic OCAs for the preparation of stereoregular polyesters (Chapter 3). The mechanistic studies of the aforementioned developments lead to the application of such a catalytic system in controlled electrochemical ROP of OCAs (Chapter 4). Such chemistry can also be translated to stereoselectively electrochemical ROP of racemic OCAs to either syndiotactic or stereoblock polyesters, allowing precise control of polyester's tacticity and sequence (Chapter 5). An overview future work has been summarized (Chapter 6). / Doctor of Philosophy / Polyesters are widely used in everyday applications ranging from clothing and packaging to agriculture and biomedicine. Different from conventional unrecyclable plastics, polyesters are usually biocompatible and biodegradable, and can be synthesized from renewable resources. A few commercially available polyesters have been approved by FDA and widely used for medical applications. However, their utility for applications that demand various mechanical and chemical properties is greatly limited by the lack of side-chain functional groups in polyesters and in their monomers—lactones. Increasing efforts have been devoted to the introduction of pendant groups along the polymer chain in order to modify and modulate the desired properties of polyesters and thereby to expand their applications. Over the last decade, O-carboxyanhydrides (OCAs) have emerged as an alternative class of highly active monomers for polyester polymerization. OCAs can be prepared from renewable source amino acids and thus have a richer range of side chain functional groups. Like lactones, OCAs can undergo ring-opening polymerization (ROP). Unfortunately, current ROP methods usually result in uncontrolled polymerization of OCAs including loss of stereoregularity, unpredictable molecular weights, or slow polymerization rate. To address the above-described polymer chemistry and materials challenges, I have been motivated to develop a new polymer chemistry knowledge base when starting my Ph.D. program. I was first involved in the development of a controlled photoredox polymerization of OCAs produces polyesters with various side chain functional groups. By using photoredox Ni/Zn/Ir catalysts, stereoregular high molecular weight polyesters can be synthesized from racemic OCAs in a rapid, controlled manner. However, this catalytic system has to be used at -20 °C despite so successful in preparing stereoblock polyesters. Encouraged by our recent success in this area, I started to work on the discovery of other transition metal complexes such as the Co complexes used in N-carboxyanhydride polymerization. Ultimately, innovative photoredox Co/Zn catalysts has been successfully developed, and applied to our protocol to achieve the controlled ROP of enantiopure OCAs under mild reaction condition (Chapter 2). The Co catalyst can replace both Ni and Ir in aforementioned photoredox system. Meanwhile, the combination of Co catalysts and various Zn/Hf complexes has also been developed to undergo photoredox ROP of racemic OCAs to efficiently produce polyesters with different microstructures (Chapter 3). Although photoredox ROP is an efficient method for synthesizing degradable polyesters, great decrease in photonic flux with the depth of the reaction medium makes it less energy efficient compared to electricity. Therefore, we then extended our protocol to electrochemical reaction, which is one of the most energy-efficient chemical reactions. The newly identified Co/Zn catalytic system can be activated by electric current to mediate rapid electrochemical ROP (eROP) of enantiopure OCAs, allowing for the synthesis of isotactic polyesters in a highly controlled manner (Chapter 4). Additionally, stereoselective eROP of racemic OCAs has been firstly achieved by using various combinations of Co and Zn/Hf complexes (Chapter 5). In summary, my research produces unique and transformative insights into the innovative photoredox and electrochemical ROP mediated by metal catalysts. Given the importance and versatility of biodegradable and biocompatible polyester materials, the chemistry invented by our team can be expected to serve as a new platform for various applications in material and biomedical engineering.