Thionoglycine as a multifunctional spectroscopic reporter of screw-sense preference in helical foldamers

Organic & Biomolecular Chemistry
Matteo De Poli, Jonathan Clayden

Abstract

A single thionoglycine (glycine thioamide, -HNCH2C(=S)-) residue inserted into a peptide foldamer provides both a pair of germinal protons for use as a (1)H NMR stereochemical probe and a chromophore giving rise to a well defined Cotton effect in CD. Comparison of the response of these two features to a local helically chiral environment validates them as independent methods for quantifying the conformational screw-sense preference of a helical oligomer, in this case a peptide made of repeated Aib units. The sign of the Cotton effect provides a measure of the sign of the screw-sense preference, while both the chemical shift separation of the anisochronous signals of the glycine CH2 group and the magnitude of the Cotton effect give an estimate of the helicity excess of the oligomer. The thionoglycine unit is readily introduced synthetically by a thionation of a BocGlyAibOMe dipeptide.

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Citations

Jul 16, 2014·Physical Chemistry Chemical Physics : PCCP·Mauro TorselloAntonino Polimeno
Jun 12, 2014·Chemical Communications : Chem Comm·Bryden A F Le Bailly, Jonathan Clayden
Dec 25, 2015·Journal of the American Chemical Society·Jennifer E JonesSimon J Webb
Sep 9, 2015·Chemical Reviews·Sundus Erbas-CakmakAlina L Nussbaumer
Mar 10, 2016·Chemical Communications : Chem Comm·Bryden A F Le Bailly, Jonathan Clayden
Feb 3, 2015·Journal of Peptide Science : an Official Publication of the European Peptide Society·Marco CrismaClaudio Toniolo
May 15, 2015·Chemical Communications : Chem Comm·Robert W NewberryRonald T Raines
May 17, 2014·Organic & Biomolecular Chemistry·Sarah J PikeJonathan Clayden
Jun 30, 2016·Biopolymers·Marta De ZottiClaudio Toniolo
Oct 13, 2018·Chemical Science·Francis G A ListerJonathan Clayden
May 1, 2018·ACS Omega·Xiao-Sheng YanYun-Bao Jiang
May 7, 2019·The Journal of Physical Chemistry Letters·Malte OppermannJan Helbing

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