Intrinsically Photoswitchable α/β Peptides toward Two‐State Foldamers |
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| Authors: | Giulia Marafon Dr. Marco Crisma Prof. Alessandro Moretto |
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| Affiliation: | 1. Department of Chemical Sciences, University of Padova, Padova, Italy;2. Institute of Biomolecular Chemistry, Padova Unit, CNR, Padova, Italy |
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| Abstract: | A simple, unsaturated, E–Z photoisomerizable β‐amino acid, (Z)‐3‐aminoprop‐2‐enoic acid, has been introduced into peptide foldamers through a one‐pot chemical coupling, based on Pd/Cu‐catalyzed olefin oxidative amidation, between two peptide segments carrying, respectively, a ‐Gly‐NH2 residue at the C‐terminus and an acryloyl group at the N‐terminus. Reversible conversion between the Z and E configurations of the 3‐aminoprop‐2‐enoic linkage was achieved photochemically. A crystallographic analysis on two model compounds shed light on the consequences, in terms of 3D structure and self‐association properties, brought about by the different configuration of the unsaturated linkage. As a proof of concept, E–Z photoisomerization of a 3‐aminoprop‐2‐enoic acid residue, inserted as the junction between two conformationally distinct peptide domains (one helical while the other β‐sheet promoter), allowed supramolecular self‐association to be reversibly turned on/off. |
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| Keywords: | chemical ligation foldamers peptidomimetics photoisomerization supramolecular chemistry |
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