| Abstract: | 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 enzyme 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. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 |
