10.1002/anie.201707086
Angewandte Chemie International Edition
COMMUNICATION
[11] a) In all kinetic experiments, either acetonitrile or DMF (<4 v/v%) was
used as co-solvent to solubilize the benzhydrylium tetrafluoroborates
and, occasionally, also the peroxides. Separate experiments in the
relevant concentration range showed that the rate constants kobs were
not affected by the content of co-solvent. b) In analogy to a procedure
used in T. Bug, H. Mayr, J. Am. Chem. Soc. 2003, 125, 12980–12986.
[12] The reactions of the peroxide anions 1 and 2 with the benzhydrylium
desolvation energies of the peroxide anions and not by their
relative basicities.[26]
From the good agreement between experimental and
calculated (by equation 1) rate constants in Table 2, we expect
that the reactivity parameters N and sN for peroxide anions
derived in this work can generally be employed for prediciting
rates of nucleophilic epoxidations (Weitz-Scheffer epoxidations).
The almost perfect match between the experimental and the
quantum chemically calculated Gibbs energies of activation
(Table 3) suggests, that the employed computational approach
including dispersion and solvent effects may be capable of
calculating activation barriers also for further types of
nucleophile-electrophile reactions.
–
tetrafluoroborate 6a-BF4 yielded the (alkylperoxy)benzhydryls 8a
(64%) and 8b (88%), respectively, which were characterized by single-
crystal x-ray crystallography. CCDC 1561460 (8b) and 1561461 (8a)
contain the supplementary crystallographic data for this paper. These
data are provided free of charge by The Cambridge Crystallographic
Data Centre (for details on the isolation and characterization of 8a and
8b see Supporting Information). Analogous reactions of the
peroxycarboxylates 4, 5c, or 5e with 6a furnished only decomposition
products.
[13] A database of reactivity parameters E, N and sN can be accessed at
Acknowledgements
[14] Previous epoxidations of benzylidenemalononitriles a) with NaOCl or
Ca(OCl)2: A. Robert, S. Jaguelin, J. L. Guinamant, Tetrahedron 1986,
42, 2275–2282; b) A. Foucaud, M. Bakouetila, Synthesis 1987, 854–
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Chem. Sect. B 2001, 40, 243–247; e) with tBuOOH and cumene
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Z. Wang, L. Wang, Eur. J. Org. Chem. 2016, 1251–1254.
We thank L’Oréal Research & Innovation (Aulnay sous Bois,
France) for financial support, Marion Sokoll (LMU) for the help
with potentiometric titrations, and Nathalie Hampel (LMU) for the
preparation of the electrophiles.
Keywords: peroxides • nucleophilicity • kinetics • linear free-
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