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An unexpected triethylsilane-triggered rearrangement of thioaurones to thioflavonols under SPPS conditions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Environmental Inorganic Chemistry, Department of Chemical and Biological Engineering, Chalmers University of Technology.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Analytical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
2008 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 49, no 42, 6033-6035 p.Article in journal (Refereed) Published
Abstract [en]

Thioaurones are converted to a mixture of thiaindenes and thioflavonols when exposed to reaction conditions employed in SPPS, that is, treatment with trifluoroacetic acid in the presence of triethylsilane.

Place, publisher, year, edition, pages
2008. Vol. 49, no 42, 6033-6035 p.
Keyword [en]
Peptidomimetics, Chromophores, Rearrangement, Reduction, Silanes, Hemithioindigo, Thioaurone
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:uu:diva-97703DOI: 10.1016/j.tetlet.2008.07.054ISI: 000259883800001OAI: oai:DiVA.org:uu-97703DiVA: diva2:172743
Available from: 2008-11-04 Created: 2008-11-04 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Photoswitchable Peptidomimetics: Synthesis and Photomodulation of Functional Peptides
Open this publication in new window or tab >>Photoswitchable Peptidomimetics: Synthesis and Photomodulation of Functional Peptides
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The secondary structure of peptides is of pivotal importance for their biological function. The introduction of photoswitchable moieties into the backbones of peptides provides a unique way of regulating their conformation using an external stimulus, i.e., light. This thesis addresses the design, synthesis, and conformational analysis of photoswitchable peptidomimetics (PSPM). Examples of photomodulation of their functional properties are given.

PSPM were prepared by incorporation of stilbene and thioaurone chromophores (switches) into dipeptides. Synthetic schemes for preparing these chromophores have been developed. Their suitability for incorporation into peptidomimetics has been demonstrated, and the resulting PSPM have been subjected to photoisomerization as well as computational and spectroscopic conformational analysis. The chromophore’s potential as a β-hairpin inducer was particularly interesting.

To investigate the factors that govern the formation of β-hairpins, a series of decapeptides were prepared. Turn regions consisting of amino acids or chromophores were combined with antiparallel peptide strands with hydrophobic side chains. Linear tryptophan zipper peptidomimetics and cyclic peptidomimetics with a second, hairpin-inducing turn region were particularly promising. Comparison between switches revealed that the more flexible stilbene is a better choice for upholding the β-hairpin conformation than the thioaurone.

The catalytic properties of an artificial hydrolase with a helix-loop-helix structure can be improved by introducing a stilbene photoswitch into the loop region. Photoisomerization regulates the catalytic activity of this peptidomimetic, and provides a means to control its aggregation state.

The activity of the enzyme Mycobacterium tuberculosis ribonucleotide reductase was realized by incorporating a stilbene moiety into a linear peptide. Here, one photoisomer proved to be an inhibitor at nM concentrations. A significantly lower effect was observed for the other isomer.

Finally, the decomposition of thioaurones, mainly to thioflavonols and thiaindenes, under conditions used for solid-phase peptide synthesis has been mapped. These findings are expected to have implications for future use of this chromophore.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2008. 70 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 565
Keyword
β-hairpin, peptidomimetics, stilbene, thioaurone, photochemistry
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-9345 (URN)978-91-554-7323-5 (ISBN)
Public defence
2008-11-27, B7:101a, BMC, Husargatan 3, Uppsala, 10:15
Opponent
Supervisors
Available from: 2008-11-04 Created: 2008-11-04 Last updated: 2010-12-15Bibliographically approved

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Bergquist, JonasGogoll, Adolf

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