aCollege of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, PR China
bSchool of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, PR China
Abstract:
The density functional theory was employed to investigate the mechanism for the cyclopropanation reactions of samarium carbenoid with an allylic alcohol. Seven competitive reaction pathways were investigated. Analysis of the calculated results shows that the models 4 and 6 have relatively low reaction barriers which suggested that the deprotonation of allylic alcohol promoted by CH3SmCH2I plays a significant important role in the cyclopropanation reaction via a samarium carbenoid. The methylene transfer and carbometalation pathways are involved in both intermolecular and intramolecular reaction pathways. On the basis of the energetics of the reaction pathways, the methylene transfer pathway is favored over the carbometalation pathway in the whole reactions. Our computational results are in good agreement with the experimental results performed by G.A. Molander and L.S. Harring.