Organic Synthesis without Stoichiometric Reagents: A Guiding Principle for Reaction Development

Abstract

A common theme of our research program is the development of new organic transformations that operate under catalytic conditions or as ligation reactions that do not require the addition of any reagents or other additives. Our catalysis program features the transient generation of reactive species from alpha-functionalized aldehydes via intramolecular redox reactions using N-heterocyclic carbenes as multifunctional catalysts. This approach makes possible the catalytic generation of enolates, homoenolates, and activated carboxylates and their application to diastereo- and enantioselective transformation. Intermolecular redox couplings are key to a general, highly chemoselective amide-forming ligation reaction and its use for oligopeptide synthesis. The concepts behind these transformation and examples of their use as well as current and future directions of our research program are presented.