jo5b01298_si_003.cif (84.26 kB)

Structure and Reactivity of Indolylmethylium Ions: Scope and Limitations in Synthetic Applications

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posted on 04.09.2015, 00:00 by Elsa Follet, Guillaume Berionni, Peter Mayer, Herbert Mayr
Eight substituted aryl­(indol-3-yl)­methylium tetrafluoroborates 3­(a–h)-BF4 and three bis­(indol-3-yl)­methylium tetrafluoroborates 3­(i–k)-BF4 have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Their reactions with π-nucleophiles 8­(a–j) (silylated enol ethers and ketene acetals) were studied kinetically using photometric monitoring at 20 °C. The resulting second-order rate constants were found to follow the correlation log k(20 °C) = sN(N + E), in which nucleophiles are characterized by the two solvent-dependent parameters N and sN, and electrophiles are characterized by one parameter, E. From the previously reported N and sN parameters of the employed nucleophiles and the measured rate constants, the electrophilicities of the indol-3-ylmethylium ions 3­(a–k) were derived and used to predict potential nucleophilic reaction partners. A discrepancy between published rate constants for the reactions of morpholine and piperidine with the (2-methyl­indol-3-yl)­phenyl­methylium ion 3h and those calculated from E, N, and sN was analyzed and demonstrated to be due to a mistake of the value reported in the literature.

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