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 SN 2 reactions followed linear relationships with Mayr nucleophilicity parameters (N/sN ) and Brønsted basicities (pKaH ) 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 SN 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 SN 2 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.

Nucleophilicities and Nucleofugalities of Thio- and Selenoethers.

Rate constants for the reactions of dialkyl chalcogenides with laser flash photolytically generated benzhydrylium ions have been measured photometrically to integrate them into the comprehensive benzhydrylium-based nucleophilicity scale. Combining these rate constants with the previously reported equilibrium constants for the same reactions provided the corresponding Marcus intrinsic barriers and made it possible to quantify the leaving group abilities (nucleofugalities) of dialkyl sulfides and dimethyl selenide. Due to the low intrinsic barriers, dialkyl chalcogenides are fairly strong nucleophiles (comparable to pyridine and N-methylimidazole) as well as good nucleofuges; this makes them useful group-transfer reagents.

Nucleophilic Reactivities of Thiophenolates.

The nucleophilic reactivities of substituted thiophenolates were determined by following the kinetics of their reactions with a series of quinone methides (reference electrophiles) in DMSO at 20 °C. The experimentally determined second-order rate constants were analyzed according to the Mayr-Patz equation log k = sN(N + E) to derive the nucleophile-specific reactivity parameters N and sN for ten thiophenolate ions.