Theoretical study on the Rh-catalyzed C−C activation of cyclopropanol to
construct diketone or monoketone
Abstract
The mechanisms of C−C activation of 1-Benzylcyclopropan-1-ol to produce
1,6-diketone have been investigated by density functional theory (DFT)
calculations. The catalyst [Cp*RhCl2]2 and additive Ag2CO3 play an
important role in controlling the selectivity. By employing
[Cp*RhCl2]2 as catalyst and Ag2CO3 as additive, the product is
1,6-diketone, whereas the β-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.