Ni-Catalyzed 1,5-Sigmatropic Ester Shift on Cyclopentadiene Rings: Regioselective Conversion of 5,5-Disubstituted Cyclopentadienes to CH2-Cyclopentadienes.

Described herein is a nickel(II)-catalyzed regioselective rearrangement of 5,5-disubstituted cyclopentadienes to fully functionalized CH2-cyclopentadienes via successive 1,5-sigmatropic shifts of the ester group on the quaternary carbon and hydrogen under mild basic conditions. The obtained CH2-cyclopentadienes were also readily applied in the preparation of highly functionalized dibenzo[e,g]azulene derivatives in two steps.