Development of new methods for ACYL C-O and C-N crosscoupling

Amide and ester bonds are ubiquitous in organic synthesis, polymers, and drug discovery; therefore the development of catalytic amide and ester bond cross-coupling reactions is of broad interest to selectively functionalize organic molecules. The use of amides and esters as acyl transfer reagents has been a burgeoning area in organic chemistry and the main challenge remains the development of new methods to selectively activate amide and ester bonds. This thesis describes our studies on: (1) the development of novel transition-metal-catalyzed transformations of amides and esters by X–C(O) (X = NR2, OR) activation; (2) the development of new amide and ester precursors for cross-coupling reactions; (3) the development of new, robust catalytic systems for acyl-cross-coupling reactions of amides and esters. Specifically, this thesis addresses the development of pentafluorophenyl esters as highly selective acylating reagents for the Suzuki-Miyaura cross-coupling using Pd-phosphine catalysis. Then, the development of twisted N-acyl-phthalimides and electronically-activated N-acylcarbazoles and N-acyl-indoles by Nlp to Ar delocalization using Pd–NHC catalyst systems for acyl cross-coupling is described. Finally, the development of cross-coupling of various amides using well-defined, air- and moisture-stable Ni–NHC complexes is described.Ph.D.Includes bibliographical reference