Di- and Triarylmethylium Ions as Probes for the Ambident Reactivities of Carbanions Derived from 5-Benzylated Meldrum’s Acid

Chemistry - A European Journal, 2014, Volume 20, Issue 35, pages 11069–11077 published on 25.08.2014
Chemistry - A European Journal
The kinetics of the reactions of carbocations with carbanions 1 derived from 5-benzyl-substituted Meldrum’s acids 1-H (Meldrum’s acid=2,2-dimethyl-1,3-dioxane-4,6-dione) were investigated by UV/Vis spectroscopic methods. Benzhydryl cations Ar2CH+ added exclusively to C-5 of the Meldrum’s acid moiety. As the second-order rate constants (kC) of these reactions in DMSO followed the linear free-energy relationship lg k=sN(N+E), the nucleophile-specific reactivity parameters N and sN for the carbanions 1 could be determined. In contrast, trityl cations Ar3C+ reacted differently. While tritylium ions of low electrophilicity (E<−2) reacted with 1 through rate-determining β-hydride abstraction, more Lewis acidic tritylium ions initially reacted at the carbonyl oxygen of 1 to form trityl enolates, which subsequently reionized and eventually yielded triarylmethanes and 5-benzylidene Meldrum’s acids by hydride transfer.
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