Hydrophenoxylation of alkynes by gold catalysts: a mini review

The field of chemistry has significantly evolved, with catalysis playing a crucial role in transforming chemical processes. From Valerius' use of sulfuric acid in the sixteenth century to modern advancements, catalysis has driven innovations across various industries. The introduction of gold as a catalyst marked a pivotal shift, expanding its applications beyond ornamentation to homogeneous catalysis. Gold's unique properties, such as its electrophilic nature and flexibility, have enabled its use in synthesizing complex molecules, including those in nanomedicine and sustainable chemical processes. The development of gold-based complexes, particularly in hydroalkoxylation and hydroamination reactions, showcases their efficiency in forming carbon-oxygen bonds under mild conditions. Recent studies on dual gold catalysis and heterobimetallic complexes further highlight gold's versatility in achieving high turnover rates and selectivity. This evolution underscores the potential of gold catalysis in advancing environmentally sustainable methodologies and enhancing the scope of modern synthetic chemistry. The debate about the nature of monogold and dual-gold catalysis is open.

DFT calculations have played a key role in promoting the activation of alkynes, in particular the hydrophenoxylation of alkynes by metal-based catalysts. They not only help identify the most efficient and selective catalysts but also aid in screening for those capable of performing a dual metal catalytic mechanism. The most commonly used functionals are BP86 and B3LYP, with the SVP and 6-31G(d) basis sets employed for geometry optimizations, and M06 with TZVP or 6-311G(d,p) basis sets used for single-point energy calculations in a solvent. Grimme dispersion correction has been explicitly added either in the solvent single point energy calculations or in the gas phase geometry optimizations or in both. To point out that M06 implicitly includes part of this dispersion scheme.