Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights

Sophie R. Thomas; Riccardo Bonsignore; Jorge Sanchez Escudero; Samuel M. Meier-Menches; Christopher M. Brown; Michael O. Wolf; Giampaolo Barone; Louis Y. P. Luk; Angela Casini

doi:10.1002/cbic.202000262

Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights

Sophie R. Thomas
, Riccardo Bonsignore
, Jorge Sanchez Escudero
, Samuel M. Meier-Menches
, Christopher M. Brown
, Michael O. Wolf
, Giampaolo Barone
, Louis Y. P. Luk (Corresponding author)
, Angela Casini (Corresponding author)

Department of Analytical Chemistry

Publications: Contribution to journal › Article › Peer Reviewed

Abstract

To gain more insight into the factors controlling efficient cysteine arylation by cyclometallated Au(III)complexes, the reaction between selected gold compounds and different peptides was investigated by high-resolution liquid chromatography electrospray ionization mass spectrometry (HR-LC-ESI-MS). The deduced mechanisms of C-S cross-coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.

Original language	English
Pages (from-to)	3071-3076
Number of pages	6
Journal	ChemBioChem: a european journal of chemical biology
Volume	21
Issue number	21
DOIs	https://doi.org/10.1002/cbic.202000262
Publication status	Published - 8 Jul 2020

Funding

S.T. acknowledges EPSRC and CDT in Catalysis for funding under grant agreement no. EP/L016443/1. R.B. acknowledges funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement no. 663830. M.O.W. and C.M.B. acknowledge funding from the Natural Sciences and Engineering Research Council of Canada (NSERC). Authors thank the analytical service provided by Thomas Williams at the Cardiff University School of Chemistry for their support and EPSRC (EP/L027240/1) for the HR-LCMS resources. L.L. acknowledges the financial support provided by BBSRC (BB/T015799/1), Leverhulme Trust (RPG-2017-195) and Royal Society (RG170187). S.M.M. acknowledges the financial support provided by the Austrian Science Fund (FWF): P33238-N. Open access funding enabled and organized by Projekt DEAL.

Austrian Fields of Science 2012

106002 Biochemistry
106023 Molecular biology
301305 Medical chemistry

Keywords

chemoselectivity
cyclometallated gold complexes
cysteine arylation
mass spectrometry
peptides
GOLD(III) COMPLEXES
PROTEIN
FUNCTIONALIZATION
CATALYSIS
TOOL

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10.1002/cbic.202000262

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Thomas, S. R., Bonsignore, R., Sanchez Escudero, J., Meier-Menches, S. M., Brown, C. M., Wolf, M. O., Barone, G., Luk, L. Y. P., & Casini, A. (2020). Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights. ChemBioChem: a european journal of chemical biology, 21(21), 3071-3076. https://doi.org/10.1002/cbic.202000262

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title = "Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights",

abstract = "To gain more insight into the factors controlling efficient cysteine arylation by cyclometallated Au(III)complexes, the reaction between selected gold compounds and different peptides was investigated by high-resolution liquid chromatography electrospray ionization mass spectrometry (HR-LC-ESI-MS). The deduced mechanisms of C-S cross-coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.",

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year = "2020",

month = jul,

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doi = "10.1002/cbic.202000262",

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Thomas, SR, Bonsignore, R, Sanchez Escudero, J, Meier-Menches, SM, Brown, CM, Wolf, MO, Barone, G, Luk, LYP & Casini, A 2020, 'Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights', ChemBioChem: a european journal of chemical biology, vol. 21, no. 21, pp. 3071-3076. https://doi.org/10.1002/cbic.202000262

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AU - Thomas, Sophie R.

AU - Bonsignore, Riccardo

AU - Sanchez Escudero, Jorge

AU - Meier-Menches, Samuel M.

AU - Brown, Christopher M.

AU - Wolf, Michael O.

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AU - Luk, Louis Y. P.

AU - Casini, Angela

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AB - To gain more insight into the factors controlling efficient cysteine arylation by cyclometallated Au(III)complexes, the reaction between selected gold compounds and different peptides was investigated by high-resolution liquid chromatography electrospray ionization mass spectrometry (HR-LC-ESI-MS). The deduced mechanisms of C-S cross-coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.

KW - chemoselectivity

KW - cyclometallated gold complexes

KW - cysteine arylation

KW - mass spectrometry

KW - peptides

KW - GOLD(III) COMPLEXES

KW - PROTEIN

KW - FUNCTIONALIZATION

KW - CATALYSIS

KW - TOOL

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IS - 21

ER -

Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au(III)Compounds: New Mechanistic Insights

Abstract

Funding

Austrian Fields of Science 2012

Keywords

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