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 2013-04-01
Year available 2013
Sub-type Article (original research)
DOI 10.1021/ja312459b
Open Access Status Not yet assessed
Volume 135
Issue 14
Start page 5242
End page 5245
Total pages 4
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Subject 1503 Catalysis
1600 Chemistry
1303 Biochemistry
1505 Colloid and Surface Chemistry
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.
Keyword Chemistry, Multidisciplinary
Q-Index Code C1
Q-Index Status Confirmed Code
Grant ID GM-66055
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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