Organic Chemistry Seminar

Our group has been involved in the design, in-situ modification, and mechanistic interrogation of secondary-sphere interactions in organocatalysis. As proof-of-concept, we modified the secondary sphere of N-heterocyclic carbenes (NHCs) using boronic acids under reaction conditions, which allowed us to control the reactivity and selectivity of the benzoin reaction and probe its mechanism. Consequently, by intercepting intermediates involved in these reactions, we were able to reroute reactivity toward mild chemoselective aldehyde deuteration. We recently demonstrated the generality of our approach through secondary-sphere modification of amino catalysts in a proline-catalyzed aldol reaction. Modifying organocatalysts in situ facilitates accessing diverse catalyst derivatives with minimal synthetic effort. The resulting data provide an exquisite opportunity for the development of machine learning strategies for reaction optimization and toward uncovering mechanistic insights to enable new reactivities.