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

Christos Tsiamantas; Xavier de Hatten; Céline Douat; Brice Kauffmann; Victor Maurizot; Hirotaka Ihara; Makoto Takafuji; Nils Metzler-Nolte; Ivan Huc

doi:10.1002/anie.201601156

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

Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6848-52. doi: 10.1002/anie.201601156. Epub 2016 Apr 21.

Authors

Christos Tsiamantas^{1

2}, Xavier de Hatten^{1

2}, Céline Douat^{1

2}, Brice Kauffmann^{3

4

5}, Victor Maurizot^{1

2}, Hirotaka Ihara⁶, Makoto Takafuji⁶, Nils Metzler-Nolte⁷, Ivan Huc^{8

9}

Affiliations

¹ University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.
² CNRS, CBMN (UMR 5248), France.
³ University of Bordeaux, Institut Européen de Chimie et Biologie (UMS3033), 2 rue Escarpit, 33600, 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, 2-39-1 Kurokami, Kumamoto, 860-8555, Japan.
⁷ Ruhr University Bochum, Faculty for Chemistry and Biochemistry, Universitätstrasse 150, 44801, Bochum, Germany.
⁸ University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France. i.huc@iecb.u-bordeaux.fr.
⁹ CNRS, CBMN (UMR 5248), France. i.huc@iecb.u-bordeaux.fr.

PMID: 27101565
DOI: 10.1002/anie.201601156

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.

Keywords: chirality; foldamers; macrocycles; remote conformational communication; thiol-disulfide exchange.

Publication types

Research Support, Non-U.S. Gov't