Entropy versus tether strain effects on rates of intramolecular 1,3-dipolar cycloadditions of N-alkenylnitrones

Krenske, Elizabeth H., Houk, K. N., Holmes, Andrew B. and Thompson, John (2011) Entropy versus tether strain effects on rates of intramolecular 1,3-dipolar cycloadditions of N-alkenylnitrones. Tetrahedron Letters, 52 17: 2181-2184. doi:10.1016/j.tetlet.2010.11.121


Author Krenske, Elizabeth H.
Houk, K. N.
Holmes, Andrew B.
Thompson, John
Title Entropy versus tether strain effects on rates of intramolecular 1,3-dipolar cycloadditions of N-alkenylnitrones
Journal name Tetrahedron Letters   Check publisher's open access policy
ISSN 0040-4039
1873-3581
Publication date 2011-04-27
Sub-type Article (original research)
DOI 10.1016/j.tetlet.2010.11.121
Volume 52
Issue 17
Start page 2181
End page 2184
Total pages 4
Place of publication Oxford, United Kingdom
Publisher Pergamon
Language eng
Abstract Intramolecular 1,3-dipolar cycloadditions of two N-alkenylnitrones are studied by means of density functional theory calculations. Cycloaddition of an acyclic 4-hexenylnitrone led to the expected isoxazolidine in 46% yield, but a 4-cycloheptenylnitrone did not react. Calculations of the transition states for cycloaddition indicate that although the cycloheptenyl nitrone has a more favorable activation entropy, the strain associated with distortion of the tethering groups into the required boat conformation disfavors the reaction of the cyclic substrate over the acyclic substrate by 8.7 kcal/mol.
Keyword Nitrone
1,3-Dipolar cycloaddition
Density functional calculations
Transition states
Ring strain
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

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