期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 14, 页码 5242-5245出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja312459b
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资金
- NIH [GM-66055]
- NSF [CHE-0548209]
- Australian Research Council [FT120100632, DP0985623]
- ARC Centre of Excellence for Free Radical Chemistry and Biotechnology
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1059084] Funding Source: National Science Foundation
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 pi 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.
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