Document Detail


Bergman cyclization of acyclic amino acid derived enediynes leads to the formation of 2,3-dihydrobenzo[f]isoindoles.
MedLine Citation:
PMID:  20718455     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Enediyne-peptide conjugates are recently recognized as useful tools in targeting various proteins, while the mechanism underlying the observed activity remains somewhat unclear. Addressing these issues, we have prepared acyclic amino acid derived enediynes and disclosed a novel thermally induced cyclization-elimination pathway. Initial formation of 1,4-benzene diradical and H-atom abstraction from an external donor is followed by S(N)2 substitution leading to 2,3-dihydrobenzo[f]isoindoles. The proposed mechanism is supported by experimental and computational data. Additionally, we showed that amino acid side chains, although placed three bonds away from acetylene terminuses, have an appreciable influence on the reactivity of studied enediynes. These results demonstrate that amino acid or peptide parts of enediyne-peptide conjugates cannot be considered as recognition elements exclusively but may also participate in various reactions through amine functionality.
Authors:
Matija Gredicak; Ivana Matanović; Boris Zimmermann; Ivanka Jerić
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  75     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2010 Sep 
Date Detail:
Created Date:  2010-09-10     Completed Date:  2011-01-11     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6219-28     Citation Subset:  IM    
Affiliation:
Division of Organic Chemistry and Biochemistry, Ruder Bosković Institute, Zagreb, 10000-HR Croatia.
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MeSH Terms
Descriptor/Qualifier:
Amino Acids / chemistry*
Cyclization
Enediynes / chemistry*
Isoindoles / chemical synthesis*,  chemistry
Molecular Dynamics Simulation
Molecular Structure
Stereoisomerism
Chemical
Reg. No./Substance:
0/2,3-dihydrobenzo(f)isoindole; 0/Amino Acids; 0/Enediynes; 0/Isoindoles

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


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