Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)-Carbon(sp3) Single Bonds.

Author(s) Jiang, S.; Yan, T.S.; Han, Y.C.; Cui, L.Q.; Xue, X.S.; Zhang, C.
Journal J Org Chem
Date Published 2017 Jun 03

We have developed an efficient method for direct formation of epoxide groups from carbon(sp2)-carbon(sp3) single bonds of -keto esters; the reaction is mediated by the water-soluble hypervalent iodine(V) reagent AIBX (5-trimethylammonio-1,3-dioxo-1,3-dihydro-15-benzo[d][1,2]iodoxol-1-ol anion). On the basis of the results of density functional theory calculations and experimental studies, we propose that the reaction proceeds by a two-stage mechanism involving dehydrogenation of the -keto ester substrates and epoxidation of the resulting enone intermediates. The rate-limiting step is abstraction of the β'-C-H (calculated free energy of activation, 24.5 kcal/mol).

DOI 10.1021/acs.joc.7b00883
ISSN 1520-6904
Citation J Org Chem. 2017.

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