Research in the Lin Lab lies within the broadly-defined field of organic chemistry, with specific emphases on synthetic electrochemistry and electrocatalysis. We develop methodologies that expand both the scope and sustainability of synthetic chemistry using the unique capabilities provided by electrochemistry. In particular, we have developed electrocatalytic approaches to encompass a variety of oxidative and reductive transformations in contexts such as alkene functionalization, strong bond activation, and asymmetric catalysis. Additionally, our program also addresses pertinent synthetic challenges in the realms of organometallic and polymer chemistry. Throughout these research areas, our work is underpinned by the rational design and mechanistic interrogation of these methodologies.
Our research objectives are underpinned by frequent use of analytical and computational tools beyond the organic chemist’s standard toolkit of spectroscopic and analytical instruments. We employ strategies such as electroanalytical chemistry, density functional theory calculations, computational structure-activity studies, and physical organic chemistry principles to drive the discovery, development, and mechanistic interrogation of our methodologies. In combination with our extensive knowledge of organic chemistry, these subdisciplines enable us to pursue both fundamental and applied advances.
Electrochemistry represents an efficient and sustainable approach to discovering and developing new organic reactions. To this end, we have developed a diverse array of electrocatalytic reactions including azidation, halogenation, alkylation, and silyation using catalytic species ranging from transition metal complexes to organocatalysts to electrode surfaces. Rigorous mechanistic understanding of the physical and chemical processes that govern these reactivities has been an essential component in the discovery and optimization of electrocatalytic systems. [Read more…]
In the realm of organic redox reactions, both photoredox catalysis and electrochemistry have been applied to a broad range of oxidative transformations. We have developed several tandem photochemical-electrochemical systems that harness the capabilities of both these modalities to effect both oxidative and reductive transformations. By coupling electrochemical activation with photoexcitation, we are able to generate and deliver unique reactive intermediates that can ultimately converge to form desired chemical motifs. [Read more…]
Reductive transformations, particularly those that require highly reducing potentials, remain an underdeveloped area within synthetic electrochemistry research. To this end, we have developed several systems with the goal of enabling electroreductive silylation and alkylation while maintaining excellent chemoselectivity and substrate compatibility. We plan to expand this strategy towards the activation of strong bonds access a broader set of electroreductive transformations. [Read more…]
Radical Redox Relay Catalysis
Owing to the high reactivity and unique selectivity patterns exhibited by organic radicals, the discovery of new reactions mediated by these open-shell intermediates can offer creative solutions to synthetic problems challenging to traditional two-electron chemistries. Our work in this area focuses on the design of catalysts that can both promote the selective generation of organic radicals and regulate their downstream reactivity to form highly functionalized chemical motifs. [Read more…]
Polymer and Materials Chemistry
Our expertise in synthetic electrochemistry also lends itself well to the synthesis of organic materials such as polymers and covalent organic frameworks. We have successfully employed electrochemistry to precisely control polymer properties such as molecular weight and dispersity. A particular interest of ours lies on exerting control over the stereochemistry and microscopic topology of the materials through catalyst design. [Read more…]