Inherent Reactivity of Spiro‐Activated Electrophilic Cyclopropanes

The kinetics of the ring‐opening reactions of thiophenolates with geminal bis(acceptor)‐substituted cyclopropanes in DMSO at 20 °C was monitored by photometric methods. The determined second‐order rate constants of the S_N2 reactions followed linear relationships with Mayr nucleophilicity parameters (N/s_N) and Brønsted basicities (pK_aH) of the thiophenolates as well as with Hammett substituent parameters (σ) for groups attached to the thiophenolates. Phenyl‐substituted cyclopropanes reacted by up to a factor of 15 faster than their unsubstituted analogues, in accord with the known activating effect of adjacent π‐systems in S_N2 reactions. Variation of the electronic properties of substituents at the phenyl groups of the cyclopropanes gave rise to parabolic Hammett relationships. Thus, the inherent S_N2 reactivity of electrophilic cyclopropanes is activated by electron‐rich π‐systems because of the more advanced C1−C2 bond polarization in the transition state. On the other hand, electron‐poor π‐systems also lower the energetic barriers for the attack of anionic nucleophiles owing to attractive electrostatic interactions.