Selective Dynamic Assembly of Disulfide Macrocyclic Helical Foldamers with Remote Communication of Handedness

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• 作者：Dr. Christos Tsiamantas ; Dr. Xavier de Hatten ; Dr. Cé ; line Douat ; Dr. Brice Kauffmann ; Dr. Victor Maurizot ; Prof. Hirotaka Ihara ; Dr. Makoto Takafuji ; Prof. Nils Metzler-Nolte and Dr. Ivan Huc
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：24
• 页码：6848-6852
• 全文大小：1892K
• ISSN：1521-3773

文摘

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