Computational study on the Rh-catalyzed C-C activation of cyclopropanol to construct diketone or monoketone

摘要

The mechanisms of C-C activation of 1-benzylcyclopropan-1-ol to produce 1,6-diketone have been investigated by density functional theory calculations. The catalyst [Cp*RhCl2](2) and additive Ag2CO3 play an important role in controlling the selectivity. By using [Cp*RhCl2](2) as the catalyst and Ag2CO3 as the additive, the product is 1,6-diketone, whereas the beta-hydride elimination product could not be obtained. The product would become monoketone in the absence of [Cp*RhCl2](2). In addition, the combination of catalyst [Cp*RhCl2](2) and additive AgOAc would also lead to monoketone. The observed selectivity could be attributed to the electronic effect.