American Chemical Society
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Intramolecular Oxyallyl–Carbonyl (3 + 2) Cycloadditions

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journal contribution
posted on 2013-04-10, 00:00 authored by Elizabeth H. Krenske, Shuzhong He, Jian Huang, Yunfei Du, K. N. Houk, Richard P. Hsung
Cycloadditions involving oxyallyl intermediates typically require an electron-rich diene or alkene, but we have discovered the first examples of the cycloaddition of heteroatom-stabilized oxyallyls onto carbonyl groups. An oxazolidinone-substituted oxyallyl undergoes chemoselective (3 + 2) cycloaddition onto the carbonyl group of a tethered dienone in preference to formation of the expected (4 + 3) cycloadduct. Density functional theory calculations indicated that the (3 + 2) cycloaddition takes place through a concerted, highly asynchronous mechanism. The transition state features simultaneous interactions of the oxyallyl LUMO with the carbonyl π and lone-pair orbitals, making this reaction “hemipseudopericyclic” (halfway between purely pericyclic and purely pseudopericyclic). Further (3 + 2) cycloadditions involving tethered phenyl ketones and a tethered enone were predicted theoretically and verified experimentally.