From a personal perspective, it is a joy to watch the larger organic synthesis community embrace and impressively develop new electrochemical methods. Those efforts are teaching us a great deal about not only electrochemical methods, but also how to best take advantage of the opportunities those methods offer. In our group, we continue to contribute to this larger enterprise by examining the role of direct electrochemical oxidation in the exploration of new oxidative cyclization strategies and the radical cation intermediates that are central to their success. These efforts have recently led to new umpolung reactions involving imine groups that are both setting the stage for introducing new levels of selectivity into the formation of non-natural amino acid building blocks and triggering new cascade types of reactions.

Interestingly, the relationship between organic synthesis and electrochemistry can also be viewed in the opposite direction with the new synthetic chemistry being developed in order to facilitate exciting opportunities to expand the scope of electrochemical experiments. For example, new synthetic methods that allow for the site-selective generation of chemical reagents have enabled the construction of complex molecular surfaces on addressable microelectrode arrays. The efforts set the stage for using the microelectrode arrays as analytical devices for rapidly screening the binding behavior of small molecule libraries with biological targets. The method offers a previously unknown level of quality control over the molecular library, and it enables the binding events to be monitored in "real-time" as they happen. However, more complex reactions leading to more complex addressable surfaces also requires better methods for characterizing what has been made and analyzing the biological interactions that arise.

Not surprisingly, the exploration of these new electrochemical tools is beginning to “give back” to the synthetic arena, and a number of preparative scale synthetic applications have now arisen based on the concept of site-selective reagent generation. For example, we have recently discovered that the strategy developed for confinement of a chemical reagent to a specific site on a microelectrode array can also be used to introduce new selectivity into solution phase chemical reactions. In the talk to be given, the interplay between organic synthesis and electrochemistry will be highlighted with an emphasis on how that interplay enables the development of new solutions to challenging synthetic problems.

References:

For reviews see Moeller, K. D. Chem. Rev. 2018, 118, 4817-4833, Jing, Q; Moeller, K. D. Accounts of Chem. Res. 2020, 53, 135-143, and Krueger, R.; Moeller, K. D. J. Org. Chem. 2021, 86, 15487-15865.