Nucleophilicity Parameters of Pyridinium Ylides and Their Use in Mechanistic Analyses

DS Allgäuer, P Mayer, H Mayr

Index: Allgaeuer, Dominik S.; Mayer, Peter; Mayr, Herbert Journal of the American Chemical Society, 2013 , vol. 135, # 40 p. 15216 - 15224

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Citation Number: 23

Abstract

Kinetics of the reactions of pyridinium, isoquinolinium, and quinolinium ylides with diarylcarbenium ions, quinone methides, and arylidene malonates (reference electrophiles) have been studied in dimethylsulfoxide solution by UV–vis spectroscopy. The second-order rate constants (log k 2) were found to correlate linearly with the electrophilicities E of the reference electrophiles, as required by the linear free-energy relationship log k 20° C= s N ...