Document Detail


Semi-synthesis of polymyxin B (2-10) and colistin (2-10) analogs employing the Trichloroethoxycarbonyl (Troc) group for side chain protection of alpha,gamma-diaminobutyric acid residues.
MedLine Citation:
PMID:  18057747     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Improved strategies for the chemical conversion of natural polymyxin B and colistin to their N-terminal analogs are reported. First, the protection of the side chains of five L-alpha,gamma-diaminobutyric acid (Dab) residues in natural polymyxin B and colistin was achieved with trichloroethoxycarbonyl (Troc), then the resulting pentakis(N gamma-Troc)-polymyxin B and pentakis(N gamma)Troc)-colistin were treated with trifluoroacetic acid (TFA) : methanesulfonic acid (MSA) : dimethylformamide (DMF) : H2O (10 : 30 : 55 : 5) at 40 degrees C in order to remove N alpha-alkanoyl-Dab(Troc)-OH selectively. The new key compounds, tetrakis(N gamma-Troc)-polymyxin B (2-10) and tetrakis(N gamma-Troc)-colistin (2-10), were obtained in 19% and 15% yields, respectively, which is higher than previous reports using trifluoroacetyl (Tfa) for tetrakis(N gamma-Tfa)-polymyxin B (2-10) and tetrakis(N gamma-Tfa)-colistin (2-10), respectively. Acylation of tetrakis(N gamma-Troc)-polymyxin B (2-10) and tetrakis(N gamma-Troc)-colistin (2-10) with various hydrophobic acids bearing aliphatic or aromatic ring structures, followed by the deprotection of Troc by Zn in AcOH, produced polymyxin B (2-10) and colistin (2-10) analogs which were used for structure-activity relationship studies. It was found that cyclohexylbutanoyl-, 4-biphenylacetyl-, and 1-adamantaneacetyl-polymyxin B (2-10) showed potent antimicrobial activity equal to that of polymyxin B against three Gram-negative bacterial strains. The lipopolysacharide (LPS) binding activity of cyclohexylbutanoyl-, 4-biphenylacetyl-, and cyclododecanecarbonyl-polymyxin B (2-10) increased greatly in comparison with that of polymyxin B (2-10). The various N alpha-acylated polymyxin B (2-10) analogs showed slightly higher antimicrobial and LPS binding activities than the corresponding N alpha-acylated colistin (2-10) analogs.
Authors:
Keiko Okimura; Kazuhiro Ohki; Yuki Sato; Kuniharu Ohnishi; Naoki Sakura
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Chemical & pharmaceutical bulletin     Volume:  55     ISSN:  0009-2363     ISO Abbreviation:  Chem. Pharm. Bull.     Publication Date:  2007 Dec 
Date Detail:
Created Date:  2007-12-06     Completed Date:  2008-01-28     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0377775     Medline TA:  Chem Pharm Bull (Tokyo)     Country:  Japan    
Other Details:
Languages:  eng     Pagination:  1724-30     Citation Subset:  IM    
Affiliation:
Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa 920-1181, Japan.
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MeSH Terms
Descriptor/Qualifier:
Acetylation
Acylation
Aminobutyric Acids / chemistry*
Anti-Bacterial Agents / chemical synthesis*,  pharmacology*
Bacteria / drug effects
Binding, Competitive / drug effects
Biopolymers / chemistry*
Chromatography, High Pressure Liquid
Colistin / analogs & derivatives*,  chemical synthesis*
Escherichia coli / metabolism
Hydrocarbons, Chlorinated / classification*
Indicators and Reagents
Lipopolysaccharides / chemistry,  metabolism
Microbial Sensitivity Tests
Polymyxin B / analogs & derivatives*,  chemical synthesis*
Spectrometry, Mass, Fast Atom Bombardment
Chemical
Reg. No./Substance:
0/Aminobutyric Acids; 0/Anti-Bacterial Agents; 0/Biopolymers; 0/Hydrocarbons, Chlorinated; 0/Indicators and Reagents; 0/Lipopolysaccharides; 1066-17-7/Colistin; 117153-91-0/gamma-poly-alpha,gamma-diaminobutyric acid; 1404-26-8/Polymyxin B

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


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