Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes.

ABSTRACT: 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_N 2 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_N 2 reactions. Variation of the electronic properties of substituents at the phenyl groups of the cyclopropanes gave rise

SUBMITTER: Justel PM 

PROVIDER: S-EPMC9298281 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature