Causation in a cascade: the origins of selectivities in intramolecular nitrone cycloadditions

Krenske, Elizabeth H., Agopcan, Sesil, Ayiyente, Viktorya, Houk, K. N., Johnson, Brian A. and Holmes, Andrew B. (2012) Causation in a cascade: the origins of selectivities in intramolecular nitrone cycloadditions. Journal of the American Chemical Society, 134 29: 12010-12015. doi:10.1021/ja300002k


Author Krenske, Elizabeth H.
Agopcan, Sesil
Ayiyente, Viktorya
Houk, K. N.
Johnson, Brian A.
Holmes, Andrew B.
Title Causation in a cascade: the origins of selectivities in intramolecular nitrone cycloadditions
Journal name Journal of the American Chemical Society   Check publisher's open access policy
ISSN 0002-7863
1520-5126
Publication date 2012-07-01
Year available 2012
Sub-type Article (original research)
DOI 10.1021/ja300002k
Open Access Status DOI
Volume 134
Issue 29
Start page 12010
End page 12015
Total pages 6
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract The factors controlling chemo-, regio-, and stereoselectivity in a cascade of reactions starting from a bis(cyanoalkenyl)oxime and proceeding via nitrone cycloadditions have been unraveled through a series of density functional theory calculations with several different functionals. Both kinetic and thermodynamic control of the reaction cascade are important, depending upon the conditions. Kinetic control was analyzed by the distortion/interaction model and found to be dictated by differences in distortions of the cycloaddends in the transition states. A new mechanism competing with that originally proposed in the application of these reactions to the histrionicotoxin synthesis was discovered in these studies.
Keyword Chemistry, Multidisciplinary
Chemistry
CHEMISTRY, MULTIDISCIPLINARY
Q-Index Code C1
Q-Index Status Provisional Code
Grant ID 5R03TW007177-02
CHE-0548209
DP0985623
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Non HERDC
School of Chemistry and Molecular Biosciences
 
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Created: Tue, 12 Feb 2013, 00:47:49 EST by Elizabeth Krenske on behalf of School of Chemistry & Molecular Biosciences