Ruthenium(II)-Catalyzed Homocoupling of α-Carbonyl Sulfoxonium Ylides Under Mild Conditions: Methodology Development and Mechanistic DFT Study.

A mild ruthenium(II)-catalyzed homocoupling of α-carbonyl sulfoxonium ylides was developed and the detailed mechanism was understood based on DFT calculations in the current report. The catalytic system utilizes the α-carbonyl sulfoxonium ylide as both the directing group for -sp C-H activation and the acylmethylating reagent for C-C coupling. Various substituents are compatible in the transformation and a variety of isocoumarin derivatives were synthesized at room temperature without any protection.

The mechanism of the gold-catalyzed intramolecular [3 + 2]-cycloaddition of 1,6-diynes: a DFT study.

The gold-catalyzed [3 + 2] cycloaddition of areneyne-yne functionalities represents one of the most efficient methodologies for the construction of tricyclic ring systems under mild conditions. In the current report, a detailed mechanistic understanding of the reaction was achieved by DFT calculations. It was found that under the catalysis of gold(i), the initial cyclization occurs more favorably between the two alkynyl moieties via the 6-exo-dig pathway other than the arene-yne addition, which is the selectivity-determining step of the whole reaction and leads eventually to the [3 + 2] cycloadduct irreversibly by following the steps of arene-cation cyclization and proton transfer.