Document Detail


Phosphinic acid pseudopeptides analogous to glutamyl-gamma-glutamate: synthesis and coupling to pteroyl azides leads to potent inhibitors of folylpoly-gamma-glutamate synthetase.
MedLine Citation:
PMID:  11463268     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Several routes to a complex phosphinate phosphapeptide analogous to the gamma-glutamyl peptide Glu-gamma-Glu have been investigated. Formation of gamma-phosphono glutamate derivatives via addition of a phosphorus-based radical to protected vinylglycine was found to be of limited value because of the elevated temperatures required. Alkylation and conjugate addition reactions of trivalent phosphorus (P(III)) species were investigated. In situ generation of bis-trimethylsilyl esters of phosphinous acids proved to be an effective route to phosphinates of modest structural complexity. However, this chemistry could not be extended to the incorporation of an amino acid moiety at the N-terminal side of the desired phosphinate. A successful synthesis of the target phosphinate phosphapeptide was effected using P(III) chemistry and dehydrohalogenation to yield an alpha,beta-unsaturated phosphinic acid ester, following which conjugate addition of diethylacetamido malonate and acid-mediated hydrolysis afforded the desired phosphinate phosphapeptide. Coupling of the unprotected phosphinate phosphapeptide with two acyl azides derived from folic acid and methotrexate led to the corresponding pteroylphosphapeptides of interest as possible mimics of tetrahedral intermediates in the reaction catalyzed by folylpolyglutamate synthetase.
Authors:
N Valiaeva; D Bartley; T Konno; J K Coward
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Publication Detail:
Type:  Journal Article; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  66     ISSN:  0022-3263     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2001 Jul 
Date Detail:
Created Date:  2001-07-20     Completed Date:  2001-08-30     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  5146-54     Citation Subset:  IM    
Affiliation:
Departments of Medicinal Chemistry and Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.
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MeSH Terms
Descriptor/Qualifier:
Azides / chemical synthesis*
Chromatography, High Pressure Liquid
Enzyme Inhibitors / chemical synthesis*,  pharmacology
Glutamates / chemistry*
Humans
Indicators and Reagents
Magnetic Resonance Spectroscopy
Mass Spectrometry
Peptide Synthases / antagonists & inhibitors*
Peptides / chemistry*
Phosphinic Acids / chemistry*
Grant Support
ID/Acronym/Agency:
CA28097/CA/NCI NIH HHS
Chemical
Reg. No./Substance:
0/Azides; 0/Enzyme Inhibitors; 0/Glutamates; 0/Indicators and Reagents; 0/Peptides; 0/Phosphinic Acids; 0/glutamyl-gamma-glutamate; EC 6.3.2.-/Peptide Synthases; EC 6.3.2.17/folylpolyglutamate synthetase

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


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