Theoretical insights into the selectivity of 1,6-enyne cycloisomerization on gold clusters: Orbital interaction role

Abstract In the present article, the mechanism of 1,6-enyne cycloisomerization catalyzed by the planar Au 8 cluster was investigated in details by means of density functional theory. The effects of the size and shape of the gold nanoclusters (Au 7-20 ) on their catalysis of 1,6-enyne cycloisomerization were also studied. The computational results indicate that the main reaction channels of the 1,6-enyne cycloisomerization on the Au 8 cluster are the 5–exo–anti–cycloisomerization, and the single cleavage pathway is slightly more feasible than the double cleavage pathway. The selectivity of 1,6-enyne cycloisomerization catalyzed by the gold clusters is controlled by the orbital interaction between the gold atoms and the carbene fragment in the migration of CH 2 group. In addition, the influence of coordinate environment of the gold atoms on adsorption energy, catalytic activity, and regio-selectivity were amply interpreted as well.