A Synthetic Strategy for the Preparation of Cyclic Peptide Mimetics Based on SET-Promoted Photocyclization Processes

A novel method for the synthesis of cyclic peptide analogues has been developed. The general approach relies on the use of SET-promoted photocyclization reactions of peptides that contain N-terminal phthalimides as light absorbing electron acceptor moieties and C-terminal α-amidosilane or α-amidocar...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2003-09, Vol.125 (35), p.10664-10671
Main Authors: Yoon, Ung Chan, Jin, Ying Xue, Oh, Sun Wha, Park, Chan Hyo, Park, Jong Hoon, Campana, Charles F, Cai, Xiaolu, Duesler, Eileen N, Mariano, Patrick S
Format: Article
Language:English
Subjects:
Biomimetic Materials - chemical synthesis
Biomimetic Materials - chemistry
Chemistry
Crystallography, X-Ray
Cyclization
Exact sciences and technology
Models, Molecular
Nuclear Magnetic Resonance, Biomolecular
Organic chemistry
Peptides
Peptides, Cyclic - chemical synthesis
Peptides, Cyclic - chemistry
Photochemistry
Phthalimides - chemical synthesis
Phthalimides - chemistry
Preparations and properties
Protein Conformation
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Summary:A novel method for the synthesis of cyclic peptide analogues has been developed. The general approach relies on the use of SET-promoted photocyclization reactions of peptides that contain N-terminal phthalimides as light absorbing electron acceptor moieties and C-terminal α-amidosilane or α-amidocarboxylate centers. Prototypical substrates are prepared by coupling preformed peptides with the acid chloride of N-phthalimidoglycine. Irradiation of these substrates results in the generation of cyclic peptide analogues in modest to good yields. The chemical efficiencies of these processes are not significantly affected by (1) the lengths of the peptide chains separating the phthalimide and α-amidosilane or α-amidocarboxylate centers and (2) the nature of the penultimate cation radical α-heterolytic fragmentation process (i.e., desilylation vs decarboxylation). An evaluation of the effects of N-alkyl substitution on the amide residues in the peptide chain showed that N-alkyl substitution does not have a major impact on the efficiencies of the photocyclization reactions but that it profoundly increases the stability of the cyclic peptide.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja030297b