Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes

Justel, Patrick M.; Stan, Alexandra; Pignot, Cedric D. and Ofial, Armin R. (2021): Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes. In: Chemistry-A European Journal, Vol. 27, No. 64: pp. 15928-15935

Abstract

The kinetics of the ring-opening reactions of thiophenolates with geminal bis(acceptor)-substituted cyclopropanes in DMSO at 20 degrees 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 Bronsted basicities (pK(aH)) of the thiophenolates as well as with Hammett substituent parameters (sigma) 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 pi-systems in S(N)2 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(N)2 reactivity of electrophilic cyclopropanes is activated by electron-rich pi-systems because of the more advanced C1-C2 bond polarization in the transition state. On the other hand, electron-poor pi-systems also lower the energetic barriers for the attack of anionic nucleophiles owing to attractive electrostatic interactions.

• Item Type: Journal article
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 0947-6539
• Language: English