Halo complexes of gold(<scp>i</scp>) containing glycoconjugate carbene ligands: synthesis, characterization, cytotoxicity and interaction with proteins and DNA model systems

Annunziata, Alfonso; Ferraro, Giarita; Cucciolito, Maria Elena; Imbimbo, Paola; Tuzi, Angela; Monti, Daria Maria; Merlino, Antonello; Ruffo, Francesco

doi:10.1039/d2dt00423b

Cited by 7 publications

(6 citation statements)

References 91 publications

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“…[12] The pivotal role of the base, the reaction mechanism, and the wide scope of NHC ligands have been studied in detail by Nolan and co-workers among others, making such gold-NHC complexes accessible to a broad audience, expanding their applications in different areas of research and consolidating their role as the foundations of organogold synthesis. The chloride ligand present on gold can be easily replaced by other halides (halogen metathesis, see Scheme 2A) [13] as well as by a wide range of organic and inorganic ligands as will be discussed in the following sections. Emphasis will be placed on how the properties of the final complexes and their applications strongly depend on the nature of the "actor" ligand.…”

Section: [Au(nhc)x] Complexes (X = Halide)mentioning

confidence: 99%

“…The [Au(IPr)OH] can also be used for the preparation of [Au(IPr)H] (14) and [Au(IPr)(NTf 2 )] (15), in reactions performed at room temperature with trimethoxysilane and bis(trifluoromethylsulfonyl)imide, respectively. The conditions used for the preparation of [Au(IPr)(NTf 2 )] are also suitable for the C À H activation of terminal alkynes such as phenylacetylene, with the production of the corresponding gold-alkynyl complex (13).…”

Section: Table 1 Synthesis Of [Au(nhc)(oh)mentioning

confidence: 99%

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Gold(I)‐N‐Heterocyclic Carbene Synthons in Organometallic Synthesis

Scattolin

Tonon

Botter

et al. 2023

Chemistry A European J

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The prominent role of gold‐N‐heterocyclic carbene (NHC) complexes in numerous research areas such as homogeneous (photo)catalysis, medicinal chemistry and materials science has prompted organometallic chemists to design gold‐based synthons that permit access to target complexes through simple synthetic steps under mild conditions. In this review, the main gold‐NHC synthons employed in organometallic synthesis are discussed. Mechanistic aspects involved in their synthesis and reactivity as well as applications of gold‐NHC synthons as efficient pre‐catalysts, antitumor agents and/or photo‐emissive materials are presented.

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Section: [Au(nhc)x] Complexes (X = Halide)mentioning

confidence: 99%

Section: Table 1 Synthesis Of [Au(nhc)(oh)mentioning

confidence: 99%

Gold(I)‐N‐Heterocyclic Carbene Synthons in Organometallic Synthesis

Scattolin

Tonon

Botter

et al. 2023

Chemistry A European J

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“…The presence of a sugar residue in the coordination sphere can also favor solubility in water and provide modulable chirality. Recently, our group extensively investigated glycoconjugation to improve the selectivity of organometallic platinum(II/IV) − and gold(I) , complexes. Notably, a Pt(II) complex containing a glycoconjugated N- heterocyclic carbene ligand, [PtMe(dmphen)(ethene)(NHC-glu)] + OTf (Figure ), was found to be extremely cytotoxic and selective to cancer cells with IC 50 values in the high nanomolar range.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules

et al. 2023

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Ruthenium(II) complexes with a three-legged piano-stool structure based on an arene ring, an N-heterocyclic carbene (NHC)-carbene ligand with a peracetylated glucose moiety and two chlorides or one bidentate ligand, were prepared and characterized by spectroscopy and crystallography. In one case, the sugar substituent is replaced by an ethyl. The chirality of the sugar results in the formation of two diastereomers that interconvert through rotations around the Ccarbene–Ru and Carene–Ru bonds. In water, the complexes undergo a series of equilibrium hydrolysis steps involving the Ru–Cl bonds. The Ru–arene bond and the sugar acetyls are also partially hydrolyzed, and the selectivity of the process is governed by the nature of the arene and the pH of the solution. The reactivity of the compounds was studied against model nucleophiles and biological macromolecules. In the former case, mass experiments demonstrated a variety of binding modes with a trend reflecting the stability in aqueous environment. In the latter case, protein crystallography was used to characterize the preferential binding sites of one of the complexes. The X-ray structure of the adduct formed upon reaction of one representative complex with hen egg white lysozyme contains a Ru center, which retains the carbene ligand, close to the side chain of Asp119. In the adduct with bovine pancreatic ribonuclease, there are two protein molecules in the asymmetric unit. In one molecule, two Ru centers are located close to the side chains of His105 and of His119, which is the protein active site. In the second molecule, only one Ru center was found in the proximity of the side chain of His105. The Ru complexes also interact with calf-thymus DNA, although without displacing the intercalating probe EB. Finally, the complexes are essentially inactive against the human ovarian carcinoma A2780 cells, the cisplatin-resistant A2780cis cells, and the human embryonic kidney HEK293T cells.

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“…As for point (a), the synthetic strategy provides robust and versatile compounds given the wide choice of carbohydrates, along with key-beneficial properties, such as chirality, tunability, hydrophilicity, and biocompatibility. Thus, Pd(II) complexes containing ligands derived from simple hexoses have been successfully applied in asymmetric allylic alkylations under unconventional conditions, , and agents based on Pt(II), − Pt(IV), and Au(I) complexes showed high selectivity and activity toward anticancer cells. Furthermore, it has also been demonstrated that the simple shift of the coordinating functions between adjacent positions of the pyranoside structure allows the creation of pseudoenantiomeric ligands, thus enabling the promotion of the same reaction with opposite enantioselectivity. − …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Chiral Iridium Complexes Bearing Carbohydrate Functionalized Pyridincarboxamide Ligands and Their Application as Catalysts in the Asymmetric Transfer Hydrogenation of α-Ketoacids in Water

et al. 2023

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Metrics & More Article Recommendations * sı Supporting Information ABSTRACT: [Cp*IrL n Cl] complexes [L 1 = (methyl-β-D-glucopyranosid-2-yl)picolinamide, 1; L 2 = (methyl-3,4,6-tri-O-acetyl-β-D-glucopyranosid-2-yl)picolinamide, 2; L 3 = (2,3,4,6-tetra-Oacetyl-β-D-glucopyranosid-1-yl)picolinamide, 3] have been synthesized and completely characterized in solution, by 1D-and 2D-NMR spectroscopy, and in the solid state, by X-ray single crystal diffractometry. Despite the chirality of the L n -moiety and metal, a single diastereoisomer is observed for L 1 (1) and L 2 (2) having a (R)-iridium configuration: the pyranose moiety is oriented in a way to minimize the interactions of the axial protons, vicinal to the amide moiety, and Cp*, with the OMe-group pointing toward the Cp*-ligand and away from Ir−Cl. Such a diastereoisomer is also favored by the establishment of an O−H•••Cl−Ir hydrogen bond (2.356 Å) and by the minimization of the steric repulsion between one acetyl moiety of L 2 and Cp* and picolinamide ligands in 1 and 2, respectively. DFT calculations computed a stabilization by more than 5.9 and 3.1 kcal/mol of this diastereoisomer with respect to other possible ones. Two interconverting diastereoisomers with different chirality at iridium are instead observed in solution for complex 3 in which −CH 2 OAc [3a, 63%, (R)] and −OAc [3b, 37%, (S)] moieties, respectively, are oriented toward Cp* and N-arm of picolinamide ligands. Consistently, DFT calculations indicate that 3a and 3b have a comparable stability (ΔE = 1.2 kcal/mol). Complexes 1−3 catalyze the asymmetric transfer hydrogenation of RC(O)C(O)OH to RCH(OH)C(O)OH [R = Ph (PGA), CH 2 Ph (PPA), CH 2 (4-OH)C 6 H 4 (HPPA)], using both HCOOH and H 3 PO 3 as hydrogen donor, in water at pH 7 (by phosphate buffer), with excellent chemoselectivity and efficiency (conversion >99%) and moderate to good enantioselectivity (30− 70% ee). Utilizing catalyst 3 instead of 2, bearing the pseudoenantiomeric L 3 of L 2 ligand, causes a reduction of the percentage of the major enantiomer (R) with PGA and an inversion of stereoselectivity from (R) to (S) with PPA and HPPA substrates.

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Halo complexes of gold(i) containing glycoconjugate carbene ligands: synthesis, characterization, cytotoxicity and interaction with proteins and DNA model systems

Abstract: New neutral carbene complexes of gold(I) [Au(Im-Me)X] (X= Cl, Au1; X= Br, Au2; X= I, Au3) have been synthesized and fully characterized by different techniques, including NMR, UV-vis absorption spectroscopy...

Cited by 7 publications

References 91 publications

Gold(I)‐N‐Heterocyclic Carbene Synthons in Organometallic Synthesis

Gold(I)‐N‐Heterocyclic Carbene Synthons in Organometallic Synthesis

Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules

Synthesis and Characterization of Chiral Iridium Complexes Bearing Carbohydrate Functionalized Pyridincarboxamide Ligands and Their Application as Catalysts in the Asymmetric Transfer Hydrogenation of α-Ketoacids in Water

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