Anodic cyclization reactions have long been a focus of the synthetic community for their ability to form densely functionalized ring systems, including those bearing quaternary carbons.  Using this chemistry has allowed the Moeller Group and numerous other research labs to develop succinct routes to natural products and synthetically useful building blocks that avoid toxic and/or unsustainable chemical oxidants.  One of the big challenges that organic electrosynthetic methods face, however, is being able to impart control over the stereochemical outcome of these cyclization reactions.  Since these cyclizations are initiated at a wide range of potentials and contain varied functional groups, we are interested in a general method for introducing stereochemistry.  Recently, the Moeller Group has shown that we can utilize a modified electrode surface to impart chemoselectivity in electrochemical oxidation reactions.  While this necessitates mediating the oxidation reactions, more importantly it also allows us to confine the reactions to the electrode surface by introducing “confining agents” into the reaction mixture.  Confining agents compete for active oxidant that has migrated from the electrode surface to the bulk solution and recycle it back to the inactive reduced form.  By forcing the oxidation to take place at the electrode surface, we can utilize interactions between a modified anode (or cathode…) and the substrate to select which groups react and, in theory, the orientation of that reaction.  Initially, we are investigating whether interactions between reticulated vitreous carbon (RVC) and polymer-coated Pt-anodes, and electron-rich aromatic systems in an electrolysis substrate can influence the chemoselectivity of cyclizations. In this way, we can learn what is needed to pin the electrolysis reaction to the electrode surface. From there, we are hoping to further extend this approach to polymer-coated electrodes bearing chiral aryl binding groups to determine whether confining an anodic cyclization to a modified electrode surface can affect the stereochemical outcome of the reaction.

Imparting reaction control in anodic cyclizations via interaction with modified electrode surfaces

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