Theoretical insights into the mechanism and origin of chemoselectivity in the catalyst- and directing group-dependent oxidative cyclization of diynes with pyridine N-oxides

Abstract

The transition-metal-catalyzed oxidative cyclization of diynes can be exploited to synthesize N-heterocycles, which are important structural motifs found in drug candidates and biologically active compounds. Herein, the mechanisms and origin...

Theoretical insights into unraveling the mechanism, selectivity patterns, and ligand effects in gold(i)-catalyzed annulations between ynamides and isoxazoles

“…The chosen level of theory, SMD-M06/6-31G(d,p)&SDD, has been demonstrated to provide reasonable predictions for the mechanism and selectivity of gold-catalyzed organic reactions. 11 All geometry optimizations were carried out without any constraints of freedom, and vibrational analyses were performed at the same theoretical level to confirm each stationary point as either a local minimum or a transition state (TS). The transition states were further verified using intrinsic reaction coordinate (IRC) 12 calculations.…”