New Synthetic Methods for the Functionalization of C-C and C-X Bonds

Aryl halides and carboxylic acids play central roles in organic synthesis with numerous important transformations requiring the use of electrophile aryl halides and radical precursor alkyl carboxylic acids. For the late-stage synthesis of medicinal products, it is crucial to develop methods that can readily activate C-X and C-C bonds in aryl halides and carboxylic acids without the use of transition-metal catalysts. In the first part, a transition-metal free functionalization of N-heterocyclic halides is described, providing access to a wide range of N-heterocyclic sulfones as well as unprecedented symmetrical N-heterocyclic sulfones and sulfides. The next part will discuss the transition-metal free functionalization of alkyl carboxylic acids under photochemical conditions. A family of acridine photocatalysts were prepared and investigated for the photo-induced acridine-catalyzed decarboxylative radical generation. The decarboxylation process was incorporated into other transformations such as olefination, C-N bond formation, sulfonylation and sulfinylation to provide access to a wide range of valuable functionalities from readily available materials carboxylic acids.