0000000001302782
AUTHOR
Sophie R. Thomas
Cyclometalated Au(III) Complexes for Cysteine Arylation in Zinc Finger Protein Domains: Towards Controlled Reductive Elimination
With the aim of exploiting the use of organometallic species for the efficient modification of proteins through C-atom transfer, the gold-mediated cysteine arylation through a reductive elimination process occurring from the reaction of cyclometalated AuIII C^N complexes with a zinc finger peptide (Cys2His2 type) is here reported. Among the four selected AuIII cyclometalated compounds, the [Au(CCON)Cl2] complex featuring the 2-benzoylpyridine (CCON) scaffold was identified as the most prone to reductive elimination and Cys arylation in buffered aqueous solution (pH 7.4) at 37 °C by high-resolution LC electrospray ionization mass spectrometry. DFT and quantum mechanics/molecular mechanics (Q…
Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au III Compounds: New Mechanistic Insights
To gain more insight into the factors controlling the efficient cysteine arylation by cyclometalated 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 deducted 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.
Carbon–Phosphorus Coupling from C^N Cyclometalated Au III Complexes
Abstract With the aim of exploiting new organometallic species for cross‐coupling reactions, we report here on the AuIII‐mediated Caryl−P bond formation occurring upon reaction of C^N cyclometalated AuIII complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2‐benzoylpyridine (CCON) scaffold was found to react with PTA (1,3,5‐triaza‐7‐phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31P{1H} NMR and HR‐ESI‐MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated Au…
C−C Cross-Couplings from a Cyclometalated Au(III) C∧ N Complex: Mechanistic Insights and Synthetic Developments
Abstract In recent years, the reactivity of gold complexes was shown to extend well beyond π‐activation and to hold promises to achieve selective cross‐couplings in several C−C and C−E (E=heteroatom) bond forming reactions. Here, with the aim of exploiting new organometallic species for cross‐coupling reactions, we report on the Au(III)‐mediated C(sp2)−C(sp) occurring upon reaction of the cyclometalated complex [Au(CCH2N)Cl2] (1, CCH2N=2‐benzylpyridine) with AgPhCC. The reaction progress has been monitored by NMR spectroscopy, demonstrating the involvement of a number of key intermediates, whose structures have been unambiguously ascertained through 1D and 2D NMR analyses (1H, 13C, 1H‐1H CO…
CCDC 1941496: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Wim T. Klooster, Simon J. Coles, Robert L. Jenkins, Didier Bourissou, Giampaolo Barone, Angela Casini|2020|Chem.-Eur.J.|26|4226|doi:10.1002/chem.201905392
CCDC 1941494: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Wim T. Klooster, Simon J. Coles, Robert L. Jenkins, Didier Bourissou, Giampaolo Barone, Angela Casini|2020|Chem.-Eur.J.|26|4226|doi:10.1002/chem.201905392
CCDC 2082255: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Mathilde Rigoulet, Christian Jandl, Alexander P��thig, Didier Bourissou, Giampaolo Barone, Angela Casini|2021|Chem.-Eur.J.|27|14322|doi:10.1002/chem.202102668
CCDC 1947336: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Wim T. Klooster, Simon J. Coles, Robert L. Jenkins, Didier Bourissou, Giampaolo Barone, Angela Casini|2020|Chem.-Eur.J.|26|4226|doi:10.1002/chem.201905392
CCDC 2082254: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Mathilde Rigoulet, Christian Jandl, Alexander Pöthig, Didier Bourissou, Giampaolo Barone, Angela Casini|2021|Chem.-Eur.J.|27|14322|doi:10.1002/chem.202102668
CCDC 2082253: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Mathilde Rigoulet, Christian Jandl, Alexander Pöthig, Didier Bourissou, Giampaolo Barone, Angela Casini|2021|Chem.-Eur.J.|27|14322|doi:10.1002/chem.202102668
CCDC 1968702: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Wim T. Klooster, Simon J. Coles, Robert L. Jenkins, Didier Bourissou, Giampaolo Barone, Angela Casini|2020|Chem.-Eur.J.|26|4226|doi:10.1002/chem.201905392
CCDC 2096758: Experimental Crystal Structure Determination
Related Article: Riccardo Bonsignore, Sophie R. Thomas, Mathilde Rigoulet, Christian Jandl, Alexander Pöthig, Didier Bourissou, Giampaolo Barone, Angela Casini|2021|Chem.-Eur.J.|27|14322|doi:10.1002/chem.202102668