Convergent diversity-oriented side-chain macrocyclization scan for unprotected polypeptides
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Pentelute_Convergent diversity.pdf
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Author(s) • • • • • •
Zou, Yekui
Spokoyny, Alexander M.
Zhang, Chi
Yu, Hongtao
Lin, Yu-Shan
Pentelute, Bradley L.
Simon, Mark
Date Issued
December 2013
Journal
Organic & Biomolecular Chemistry
Publisher
Royal Society of Chemistry, The
Citation
Zou, Yekui, Alexander M. Spokoyny, Chi Zhang, Mark D. Simon, Hongtao Yu, Yu-Shan Lin, and Bradley L. Pentelute. “Convergent Diversity-Oriented Side-Chain Macrocyclization Scan for Unprotected Polypeptides.” Org. Biomol. Chem. 12, no. 4 (2014): 566–573.
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Author's final manuscript
Abstract
Here we describe a general synthetic platform for side-chain macrocyclization of an unprotected peptide library based on the S[subscript N]Ar reaction between cysteine thiolates and a new generation of highly reactive perfluoroaromatic small molecule linkers. This strategy enabled us to simultaneously “scan” two cysteine residues positioned from i, i + 1 to i, i + 14 sites in a polypeptide, producing 98 macrocyclic products from reactions of 14 peptides with 7 linkers. A complementary reverse strategy was developed; cysteine residues within the polypeptide were first modified with non-bridging perfluoroaryl moieties and then commercially available dithiol linkers were used for macrocyclization. The highly convergent, site-independent, and modular nature of these two strategies coupled with the unique chemoselectivity of a S[subscript N]Ar transformation allows for the rapid diversity-oriented synthesis of hybrid macrocyclic peptide libraries with varied chemical and structural complexities.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c3ob42168f