Pericyclic reactions in the electronic ground state may be initiated by down-chirped pump-dump sub-pulses of an optimal laser pulse, in the ultraviolet (UV) frequency and sub-10 femtosecond (fs) time domain. This is demonstrated by means of a quantum dynamics model simulation of the Cope rearrangement of Semibullvalene. The laser pulse is designed by means of optimal control theory, with detailed analysis of the mechanism. The theoretical results support the recent experimental initiation of a pericyclic reaction. The present approach provides an important step towards monitoring asynchronous electronic fluxes during synchronous nuclear pericyclic reaction dynamics, with femto-to-attosecond time resolution, as motivated by the recent prediction of our group.