DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

Abstract

The DFT calculation of the B3LYP level was carried out to explore the reaction mechanism of the synthesis of spirocyclo[4, 5]decane skeleton by gold-catalyzed allenyl compounds. The more accurate energy under the CH3CN solvent in the experiment is calculated by the single point energy of the SMD model. Computational studies have shown that the reaction consists of three main steps: intramolecular cycloaddition of the end group carbon atoms of allenyl and vinyl groups, the semipinacol rearrangement process in which the four-membered ring is reconstructed into the five-membered ring, the elimination reaction releases the catalyst and obtains the product. The calculation results show that Zheng et al. reported that the gold-catalyzed synthesis reaction can easily occur under the experimental conditions due to its low activation free energy (12.42–16.79 kcal/mol). Furthermore, it was found that the MOMO(CH2)2 substituent has higher reactivity than the corresponding reactant of the phenyl substituent.