Syntheses of Atypically Fluorinated Peptidyl Macrocycles through Sequential Vinylic Substitutions
Tomoyuki Tsunemi1,2, Salvador J Bernardino1, Angel Mendoza1
1Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA.
Abstract:
Small peptides containing combinations of cysteine, tyrosine, histidine, and serine residues react with octafluorocyclopentene (OFCP) to afford atypically structured macrocycles through successive vinylic substitutions. The reactions proceed rapidly in air at 0 °C and are tolerant of spectating tryptophan, asparagine, glutamine, and threonine residues. Hexapeptides of consensus sequence YXCXXC displace four fluorine atoms from OFCP to generate fluorinated macrobicyclic compounds that display dual-turn surfaces. The method provides facile access to a wide range of previously unknown heterocyclic structures.
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