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J Org Chem. 2017 Feb 17;82(4):2011-2017. doi: 10.1021/acs.joc.6b02844. Epub 2017 Feb 6.

Nucleophilicity Parameters of Arylsulfonyl-Substituted Halomethyl Anions.

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Department Chemie, Ludwig-Maximilians-Universität München , Butenandtstrasse 5-13, Haus F, 81377 München, Germany.


The rates of the reactions of the arylsulfonyl-substituted carbanions carrying α-chloro and α-bromo substituents (1a-e) with quinone methides 2a-g and benzylidenemalonates 2h and 2i in DMSO were determined photometrically at 20 °C. The reactions were performed under pseudo-first-order conditions, and the second-order rate constants were obtained as the slopes of the plots of the pseudo-first-order rate constants versus the concentrations of the reactants used in excess. The second-order rate constants correlate linearly with the parameters E of the reference electrophiles according to the linear free energy relationship log k2(20 °C) = sN(N + E), which allowed us to derive the nucleophile-specific parameters N and sN of carbanions 1a-e. The resulting nucleophilicity parameters N (23 < N < 29) reveal the title compounds to be among the most reactive nucleophiles so far integrated on our comprehensive nucleophilicity scale.


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