Hetero-cope rearrangements of nitrosobutenes. DFT studies of thermal and acid-catalyzed reactions.
[Structure: see text] Density functional theory studies of the hetero-Cope reactions of 4-nitroso-1-butenes and nitrosobicyclo[2.2.2]hexenes are reported. The reactions proceed via concerted mechanisms. The electron-withdrawing methoxycarbonyl group alpha- to the nitroso group decreases the activation barrier. Lewis acids such as SbF5 and TiCl4 accelerate the reactions, as has been found experimentally by Zakarian and Lu.
Jabbari
Arash
A
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569.
Houk
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