THE ROLE OF LIGANDS IN PD-CATALYZED C-X COUPLING AND C-H FUNCTIONALIZATION REACTIONS

Abstract

LIGAND SELECTION IS AN IMPORTANT ASPECT OF PALLADIUM-CATALYZED CROSS-COUPLING REACTION. HERE THE ROLE OF LIGANDS IN PD-CATALYZED C-X COUPLING AND C-H FUNCTIONALIZATION REACTIONS IS EXPLORED. THE ROLE OF LIGANDS IN THE OXIDATIVE ADDITION OF HALOHETEROCYCLES TO PD(0) IS STUDIED AND THE UNDERLYING INTERACTION BETWEEN PD AND HETEROATOM IS DISCUSSED. THE ROLE OF LIGANDS IN THE PD-CATALYZED C-S BOND FORMATION IN ELIMINATING RESTING STATES WAS INVESTIGATED. THESE RESTING STATES (INTERMEDIATES WITH STRONG PD-S BONDS THAT EXIST OUTSIDE OF THE CATALYTIC CYCLE) WERE SYNTHESIZED, AND THEORETICAL PREDICTION OF NMR WAS EXPLORED FOR THE CHARACTERIZATION OF REACTION SPECIES. NEXT, THE STABILIZING EFFECT OF FERROCENYL PHOSPHINE LIGAND IN PENTACOORDINATED PD(II) COMPLEX WAS STUDIED. FINALLY, THE PD-CATALYZED DIRECT ARYLATION OF HETEROCYCLES VIA C-H ACTIVATION WAS STUDIED. HERE WE FOCUSED ON THE MECHANISM OF THE DIRECT ARYLATION OF FURAN WITH VARIOUS LIGANDS; TWO MECHANISMS WERE STUDIED COMPUTATIONALLY: