Density function studies on the PtCl2-catalyzed asymmetric cycloisomerization reaction of hydroxylated enynes

摘要

The PtCl2-catalyzed asymmetric cycloisomerization reaction of hydroxylated enynes was studied using density functional theory (DFT). All structures have been optimized completely at the B3LYP/6-311G(d,p) level. As shown, the cycloisomerization reaction is exothermic. The cycloisomerization reaction mainly undergoes the formation of catalyst-hydroxylated enyne coordination, the asymmetric cyclopropyl platinum carbene, catalyst-cyclopropyl enol coordination, and catalyst-cyclopropyl ketone coordination. The chirality-limiting step for the asymmetric cycloisomerization reaction is the formation of the asymmetric cyclopropyl platinum carbene, and the rate-determining step for this reaction is the formation of the catalyst-cyclopropyl ketone coordination. The dominant products predicted theoretically are (R,S) -syn_5a, in agreement with the experiment.