Kinetics of Electrophilic Fluorinations of Enamines and Carbanions: Comparison of the Fluorinating Power of N-F Reagents

Journal of the American Chemical Society
Daria S TimofeevaHerbert Mayr

Abstract

Kinetics of the reactions of enamines and carbanions with commonly used fluorinating reagents, N-fluorobenzenesulfonimide (NFSI), N-fluoropyridinium salts, Selectfluor, and an N-fluorinated cinchona alkaloid, have been investigated in acetonitrile. The reactions follow second-order kinetics, and from the measured rate constants one can derive that the fluorinations proceed via direct attack of the nucleophiles at fluorine, not by SET processes. Correlations of the fluorination rates with the p KaH values of the nucleofugal leaving groups and the calculated fluorine plus detachment energies are discussed. The rate constants for the reactions with deoxybenzoin-derived enamines follow the linear free energy relationship log k2(20 °C) = sN( N + E) which allows the empirical electrophilicity parameters E for these fluorinating agents to be derived from the measured rate constants and the tabulated N and sN parameters for the nucleophiles. Though the deviations of the measured rate constants from those calculated by this relationship are larger than for reactions of Csp2-centered electrophiles with nucleophiles, it is shown that the electrophilicity parameters E reported in this work are able to rationalize known fluorination reactio...Continue Reading

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Citations

Feb 7, 2019·Chemistry : a European Journal·Susanna H WoodDavid J Nelson
Oct 11, 2019·Angewandte Chemie·Antonio TogniErick M Carreira
Apr 9, 2020·Chemistry : a European Journal·Neshat RozatianGraham Sandford
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Feb 29, 2020·Chemical Science·Neshat RozatianDavid R W Hodgson
Dec 29, 2020·Chemical Communications : Chem Comm·Neshat Rozatian, David R W Hodgson
Aug 14, 2021·Beilstein Journal of Organic Chemistry·Teruo UmemotoGerald B Hammond
Apr 28, 2020·Journal of the American Chemical Society·Zhen LiHerbert Mayr
Apr 25, 2020·The Journal of Organic Chemistry·Tobias Schnitzer, Helma Wennemers
Jan 29, 2019·Journal of the American Chemical Society·Gabriele PupoVéronique Gouverneur
Jan 30, 2020·The Journal of Organic Chemistry·Aaron MoodDavid L Van Vranken
Jul 25, 2019·The Journal of Organic Chemistry·Lin TangXiantao Ma
Nov 20, 2019·Journal of the American Chemical Society·Zhonglin TaoScott E Denmark
Nov 16, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·William ErbFlorence Mongin

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