Document Detail

The kinetics and mechanism of the acid-catalysed detritylation of nucleotides in non-aqueous solution.
MedLine Citation:
PMID:  19081945     Owner:  NLM     Status:  MEDLINE    
The kinetics and mechanism of the deprotection (detritylation) of 5'-O-(4,4'-dimethoxytrityl)-2'-deoxythymidine nucleoside catalysed by dichloroacetic acid to give a 4,4'-dimethoxytrityl carbocation have been studied in toluene, dichloromethane and acetonitrile. There is little or no effect of solvent polarity on the equilibrium and rate constants. Entropies of activation are highly negative approximately -105 J K(-1) mol(-1) and similarly show little variation with solvent. Addition of small amounts of water to the reaction medium reduces the detritylation rate, presumably through its effect on the solution acidity. All observations are compatible with detritylation occurring through a concerted general acid-catalysed mechanism rather than a stepwise A1 process.
Mark A Russell; Andrew P Laws; John H Atherton; Michael I Page
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Publication Detail:
Type:  Journal Article     Date:  2008-11-06
Journal Detail:
Title:  Organic & biomolecular chemistry     Volume:  7     ISSN:  1477-0539     ISO Abbreviation:  Org. Biomol. Chem.     Publication Date:  2009 Jan 
Date Detail:
Created Date:  2008-12-16     Completed Date:  2009-04-24     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101154995     Medline TA:  Org Biomol Chem     Country:  England    
Other Details:
Languages:  eng     Pagination:  52-7     Citation Subset:  IM    
Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, Huddersfield, UK HD1 3DH.
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MeSH Terms
Acids / chemistry
Alcohols / chemistry
Dichloroacetate / chemistry
Dose-Response Relationship, Drug
Magnetic Resonance Spectroscopy
Models, Chemical
Molecular Structure
Nucleotides / chemistry*
Solvents / chemistry
Water / chemistry
Reg. No./Substance:
0/Acids; 0/Alcohols; 0/Nucleotides; 0/Solutions; 0/Solvents; 13425-80-4/Dichloroacetate; 7732-18-5/Water

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

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