In the first, we have been examining both radical cation and radical intermediates that are generated under net oxidative conditions. The reactions can be used to generate a wide variety of new bonds and ring systems. Recently, we have been focusing on two aspects of the reactions. First, how the reactions can be best incorporated into a synthetic sequence so that either radical cation or radical pathways can be utilized. The key is the development of a rapid means to generate either enol ether or endiol substrates for the electrolysis and then a study of the subsequent reactions (Scheme 1). Second, we have been examining how mechanistic insight into the nature of the reactive intermediates generated can be used to overcome synthetic barriers that have in the past limited use of the reactions.
In the second method to be discussed, electrochemistry and the ability it offers to generate and control new umpolung reactions is being used to conduct the total synthesis of complex molecular surfaces. The reactions range from transformations that convert synthetically optimized surfaces for use on microelectrode arrays into surfaces optimized for subsequence signaling studies (Scheme 2) to methods for the diversification of molecular scaffolds on an array. All of the reactions utilize electrochemical methods to shape the way synthetic challenges are addressed.
In the talk to be given, selected examples from both methods will be used to illustrate how a basic understanding of electrochemical reactions can be used to solve a diverse array of synthetic challenges.