Document Detail


Synthesis and biological evaluation of DL-4,4-difluoroglutamic acid and DL-gamma,gamma-difluoromethotrexate.
MedLine Citation:
PMID:  8568828     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
DL-4,4-Difluoroglutamic acid (DL-4,4-F2Glu) and its methotrexate analogue, DL-gamma,gamma-difluoromethotrexate (DL-gamma,gamma-F2MTX), were synthesized and evaluated as alternate substrates or inhibitors of folate-dependent enzymes. Synthesis of DL-4,4-F2Glu involved the nitroaldol reaction of ethyl nitroacetate with a difluorinated aldehyde ethyl hemiacetal as a key step. Attempted ligation of DL-4,4-F2Glu to methotrexate (MTX), catalyzed by human folylpoly-gamma-glutamate synthetase (FPGS), revealed that DL-4,4-F2Glu is a poor alternate substrate. DL-gamma,gamma-F2MTX was synthesized by a route proceeding through N-[4-(methylamino)benzoyl]-4,4-difluoroglutamic acid di-tert-butyl ester followed by alkylation with 6-(bromomethyl)-2,4-pteridinediamine hydrobromide. DL-gamma,gamma-F2MTX was found to be neither a substrate nor an inhibitor of human FPGS. The fluorinated analogue of MTX, however, inhibits DHFR and cell growth with the same potency as MTX.
Authors:
T Tsukamoto; T Kitazume; J J McGuire; J K Coward
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Publication Detail:
Type:  Journal Article; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Journal of medicinal chemistry     Volume:  39     ISSN:  0022-2623     ISO Abbreviation:  J. Med. Chem.     Publication Date:  1996 Jan 
Date Detail:
Created Date:  1996-03-01     Completed Date:  1996-03-01     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  9716531     Medline TA:  J Med Chem     Country:  UNITED STATES    
Other Details:
Languages:  eng     Pagination:  66-72     Citation Subset:  IM    
Affiliation:
Department of Medicinal Chemistry, University of Michigan, Ann Arbor 48109, USA.
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MeSH Terms
Descriptor/Qualifier:
Aminopterin / metabolism
Cell Division / drug effects
Cell Line
Chromatography, High Pressure Liquid
Folic Acid Antagonists / chemical synthesis*,  metabolism,  pharmacology
Glutamates / chemical synthesis*,  pharmacology*
Glutamic Acid / metabolism
Humans
Kinetics
Magnetic Resonance Spectroscopy
Methotrexate / analogs & derivatives*,  chemical synthesis,  metabolism,  pharmacology
Molecular Structure
Peptide Synthases / antagonists & inhibitors,  metabolism
Tetrahydrofolate Dehydrogenase / metabolism
Tumor Cells, Cultured
Grant Support
ID/Acronym/Agency:
CA13038/CA/NCI NIH HHS; CA16056/CA/NCI NIH HHS; CA28097/CA/NCI NIH HHS
Chemical
Reg. No./Substance:
0/Folic Acid Antagonists; 0/Glutamates; 0/gamma,gamma-difluoromethotrexate; 130835-20-0/4,4-difluoroglutamic acid; 54-62-6/Aminopterin; 56-86-0/Glutamic Acid; 59-05-2/Methotrexate; EC 1.5.1.3/Tetrahydrofolate Dehydrogenase; EC 6.3.2.-/Peptide Synthases; EC 6.3.2.17/folylpolyglutamate synthetase
Comments/Corrections
Erratum In:
J Med Chem 1996 Sep 27;39(20):4134

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


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