Selective Dynamic Assembly of Disulfide Macrocyclic Helical Foldamers with Remote Communication of Handedness |
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| Authors: | Dr. Christos Tsiamantas Dr. Xavier de Hatten Dr. Céline Douat Dr. Brice Kauffmann Dr. Victor Maurizot Prof. Hirotaka Ihara Dr. Makoto Takafuji Prof. Nils Metzler‐Nolte Dr. Ivan Huc |
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| Affiliation: | 1. University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, Pessac, France;2. CNRS, CBMN (UMR 5248), France;3. University of Bordeaux, Institut Européen de Chimie et Biologie (UMS3033), Pessac, France;4. CNRS, IECB (UMS 3033), Pessac, France;5. INSERM, IECB (US 001), Pessac, France;6. Kumamoto University, Department of Applied Chemistry and Biochemistry, Kumamoto, Japan;7. Ruhr University Bochum, Faculty for Chemistry and Biochemistry, Bochum, Germany |
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| Abstract: | Disulfide bridge formation was investigated in helical aromatic oligoamide foldamers. Depending on the position of thiol‐bearing side chains, exclusive intramolecular or intermolecular disulfide bridging may occur. The two processes are capable of self‐sorting, presumably by dynamic exchange. Quantitative assessment of helix handedness inversion rates showed that bridging stabilizes the folded structures. Intermolecular disulfide bridging serendipitously yielded a well‐defined, C2‐symmetrical, two‐helix bundle‐like macrocyclic structure in which complete control over relative handedness, that is, helix–helix handedness communication, is mediated remotely by the disulfide bridged side chains in the absence of contacts between helices. MM calculations suggest that this phenomenon is specific to a given side chain length and requires disulfide functions |
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| Keywords: | chirality foldamers macrocycles remote conformational communication thiol-disulfide exchange |
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