Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions

Krenske, Elizabeth H., He, Shuzhong, Huang, Jian, Du, Yunfei, Houk, K. N. and Hsung, Richard P. (2013) Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions. Journal of the American Chemical Society, 135 14: 5242-5245. doi:10.1021/ja312459b

Author Krenske, Elizabeth H.
He, Shuzhong
Huang, Jian
Du, Yunfei
Houk, K. N.
Hsung, Richard P.
Title Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions
Journal name Journal of the American Chemical Society   Check publisher's open access policy
ISSN 0002-7863
Publication date 2013-04
Sub-type Article (original research)
DOI 10.1021/ja312459b
Volume 135
Issue 14
Start page 5242
End page 5245
Total pages 4
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Abstract 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.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
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