3 years ago

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

Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)–Carbon(sp3) Single Bonds
Shan Jiang, Yong-Chao Han, Xiao-Song Xue, Li-Qian Cui, Chi Zhang, Tai-Shan Yan
We have developed an efficient method for direct formation of epoxide groups from carbon(sp2)–carbon(sp3) single bonds of β-keto esters; the reaction is mediated by the water-soluble hypervalent iodine(V) reagent AIBX (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ5-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 β-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).

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00883

DOI: 10.1021/acs.joc.7b00883

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