Document Detail

Probing persistent intramolecular C-H...X (X = O, S, Br, Cl, and F) bonding in solution using benzyl Meldrum's acid derivatives.
MedLine Citation:
PMID:  19113820     Owner:  NLM     Status:  MEDLINE    
Persistent intramolecular interactions between acidic C-H hydrogens and a variety of acceptors (X) (X = O, S, Br, Cl, and F) in solution were probed by (1)H NMR experiments, using 5-benzyl Meldrum's acid derivatives. To bring about formation of intramolecular C-H...X bonding, ortho-substituted benzyl Meldrum's acids were designed, for which hydrogen bonding occurred through a six-membered ring. Introduction of substituents on the aromatic moiety and in the tether allowed variation of electronic and steric factors. The superior acidity of Meldrum's acids impacted the ability of the C-H hydrogen to engage in nonclassical C-H...X bonds and drove the conformational properties of benzyl Meldrum's acid, in combination with steric factors, namely A(1,3)-allylic strain. Further understanding of intramolecular C-H...X bonds was gained by characterization of benzyl Meldrum's acids in the solid state, by X-ray analysis, and by the conformation correlated to the observations made in solution.
Eric Fillion; Ashraf Wilsily; Dan Fishlock
Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  74     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2009 Feb 
Date Detail:
Created Date:  2009-01-30     Completed Date:  2009-06-23     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1259-67     Citation Subset:  IM    
Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
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MeSH Terms
Benzyl Compounds / chemistry*
Dioxanes / chemistry*
Ethers / chemistry
Hydrocarbons, Halogenated / chemistry
Hydrogen Bonding
Magnetic Resonance Spectroscopy / methods
Molecular Conformation
Sulfides / chemistry
Reg. No./Substance:
0/Benzyl Compounds; 0/Dioxanes; 0/Ethers; 0/Hydrocarbons, Halogenated; 0/Solutions; 0/Sulfides; 2033-24-1/Meldrum's acid

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

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