Yanhong An, Cai-hong Cheng, Ben Pan
Jul 1, 2012
Citations
0
Influential Citations
11
Citations
Journal
European Journal of Organic Chemistry
Abstract
DFT investigations were employed to explore the complete reaction mechanism of the nickel-catalyzed [3+2+2] cocyclization of ethyl cyclopropylideneacetate and alkynes. The lowest-energy pathway involves the formation of a π complex between the methylenecyclopropane moiety and the nickel atom and occurs through a sequence of ring-opening and ring-closing reactions with C–C bond formation as the rate-determining step. The crucial conversion of nickelacycloheptadiene to an eight-membered nickelacycle was suggested to happen in a stepwise mechanism instead of the previously proposed cyclopropenyl–butenyl rearrangement.