Lessons from an Array: Using an Electrode Surface to Control the Selectivity of a Solution-Phase Chemical Reaction.

Electrochemistry offers a variety of novel means by which selectivity can be introduced into synthetic organic transformations. In the work reported, it is shown how methods used to confine chemical reactions to specific sites on a microelectrode array can also be used to confine a preparative reaction to the surface of an electrode inserted into a bulk reaction solution. In so doing, the surface of a modified electrode can be used to introduce new selectivity into a preparative reaction that is not observed in the absence of either the modified electrode surface or the effort to confine the reaction to that surface. The observed selectivity can be optimized in the same way that confinement is optimized on an array and is dependent on the nature of the functionalized surface.