Document Detail


Effects of Alkyl Groups in the Rate-Determining Step of the Baeyer-Villiger Reaction of Phenyl Alkyl Ketones: A Quantum Chemistry Study.
MedLine Citation:
PMID:  22738150     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
In this work, the substituent effect of several alkyl groups (-CH3; -CH2CH3; -CH2CH2CH3; -CH(CH3)2; -C6H11; -C(CH3)3) in the rate-determining step of the catalyzed Baeyer-Villiger reaction of phenyl alkyl ketones with performic (PFA) and trifluoroperacetic (TFPAA) acids are studied in detail, within the density functional theory framework. Our results shown that the substituent effects are more pronounced in the migration step Gibbs free energy barriers than in the corresponding addition step, making possible a change in the rate-determining step (RDS) of the reaction, as observed in the oxidation of phenyl tert-butyl ketone with both peracids. The effect of the acid/peracid pair used is also analyzed. The comparison of BV reactions using different acid-peracid pairs demonstrates that the addition step is less susceptible to their natures due to the opposite effects of acid strength and nucleophilicity of the peracid. The effect of the acid-peracid pair is much more pronounced in the migration step because it only depends on the leaving ability of the acid, which in turn depends on its strength.
Authors:
Lino Reyes; Celestino Díaz-Sánchez; Cristina Iuga
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-6-27
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  -     ISSN:  1520-5215     ISO Abbreviation:  -     Publication Date:  2012 Jun 
Date Detail:
Created Date:  2012-6-28     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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