Cyclopalladation of 3-methoxyimino-2-phenyl-3H-indoles

López, Concepción; González, Asensio; Moya, Carlos; Bosque, Ramón; Soláns, Xavier; Font-Bardı́a, Mercè

doi:10.1016/j.jorganchem.2008.05.043

Cited by 10 publications

(11 citation statements)

References 68 publications

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“…According to previous studies [59,60], these observations suggested the existence of a σ(M-C 2′ ) bond and the presence of five membered ring metallacycle in 4c and 5c.…”

mentioning

confidence: 60%

Platinum(II) and palladium(II) complexes with (N,N′) and (C,N,N′)− ligands derived from pyrazole as anticancer and antimalarial agents: Synthesis, characterization and in vitro activities

Quirante

Ruíz

González

et al. 2011

Journal of Inorganic Biochemistry

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The study of the reactivity of three 1-(2-dimethylaminoethyl)-1H-pyrazole derivatives of general formula [1-(CH 2 ) 2 NMe 2 }-3,5-R 2 -pzol] {where pzol represents pyrazole and R_H (1a), Me (1b) (5c)}. Compounds 4c and 5c arise from the orthometallation of the 3-phenyl ring of ligand 1c. Complex 2a has been further characterized by X-ray crystallography. Ligands and complexes were evaluated for their in vitro antimalarial against Plasmodium falciparum and cytotoxic activities against lung (A549) and breast (MDA MB231 and MCF7) cancer cellular lines. Complexes 2a-2c and 5c exhibited only moderate antimalarial activities against two P. falciparum strains (3D7 and W2). Interestingly, cytotoxicity assays revealed that the platinacycle 4c exhibits a higher toxicity than cisplatin in the three human cell lines and that the complex 2a presents a remarkable cytotoxicity and selectivity in lung (IC 50 = 3 μM) versus breast cancer cell lines (IC 50 N 20 μM). Thus, complexes 2c and 4c appear to be promising leads, creating a novel family of anticancer agents. Electrophoretic DNA migration studies in presence of the synthesized compounds have been performed, in order to get further insights into their mechanism of action.

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“…According to previous studies [59,60], these observations suggested the existence of a σ(M-C 2′ ) bond and the presence of five membered ring metallacycle in 4c and 5c.…”

mentioning

confidence: 60%

Platinum(II) and palladium(II) complexes with (N,N′) and (C,N,N′)− ligands derived from pyrazole as anticancer and antimalarial agents: Synthesis, characterization and in vitro activities

Quirante

Ruíz

González

et al. 2011

Journal of Inorganic Biochemistry

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“…This arrangement of rings allows intramolecular hydrogen contacts between the heteroatoms of the "=NOMe" unit and the hydrogen atoms H10 and H5 [distances N2•••H10 = 2.578Å and O2•••H5 = 2.521Å]. These short contacts, which reduce the flexibility of the pendant arm, were also observed in the crystal structures of the cyclometallated compounds containing Pd(II) or Ru(II) as well as in the transand cisisomers of the Pt(II) complexes (A-C) shown in Figure 2 and appear to be characteristic of this family of ligands [21][22][23]. Figure S2).…”

Section: Description Of the Crystal Structures Of Compounds 2a 3a Anmentioning

confidence: 66%

“…In the IR spectra of the new Pd(II) complexes the position of the band due to the stretching of the exocyclic >C=N− group was practically identical to those of the parent free ligands and compounds A-C presented in Figure 1 [21][22][23] indicating that a) the N oxime atom was not bound to the Pd(II) atom and b) the oxime unit adopted the anti-(E) form. X-ray diffraction studies of compounds 2a, 3a and 3b (see below), confirmed these findings.…”

Section: Scheme 1 Synthesis Of Compounds 2a-2c and 3a-3c And Atom Numentioning

confidence: 79%

“…Mono-, di-, and even polymeric Pd(II), Zn(II), Cd(II), Co(II), complexes derived from 2-diformylmethylene-3,3-dimethylindole have been reported by Prof. Kaledi's group [19,20]. Some years ago, we focused our interest on 3-methoxyimino-2-phenyl-3H-indoles and the results obtained so far revealed not only that they may act as an N-donor group ( Figure 1A) [21,22] or as a bidentate [C(sp 2 , phenyl),N] − ligand ( Figure 1B,C) [21][22][23] but also, that the resulting complexes exhibit interesting properties and biological activities. For instance, compounds A and B are more potent cytotoxic agents than their parent free ligands and even than cisplatin in MCF-7 and MDA-MB231 breast cancer cell lines [21,23].…”

Section: Introductionmentioning

confidence: 99%

“…Some years ago, we focused our interest on 3-methoxyimino-2-phenyl-3H-indoles and the results obtained so far revealed not only that they may act as an N-donor group ( Figure 1A) [21,22] or as a bidentate [C(sp 2 , phenyl),N] -ligand (Figure 1 B,C) [21][22][23] but also, that the resulting complexes exhibit interesting properties and biological activities. For instance, compounds A and B are more potent cytotoxic agents than their parent free ligands and even than cisplatin in MCF-7 and MDA-MB231 breast cancer cell lines [21,23]. Despite the increasing interest on: a) novel transition metal complexes with indole ligands and especially the 2-sustituted-3H-indoles [18][19][20], b) the role of Pd(II) in heterocyclic chemistry and in C-C bond formation (stoichiometric or catalytic) [24][25][26][27] and, c) the relevance of "Pd(II)-allyl compounds" in homogeneous catalysis and their exciting solution behavior [25][26][27][28][29][30][31][32][33][34][35], Pd(II) compounds containing simultaneously "2-phenylindole" units and η 3 -allyl ligands still remain unknown.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, Solution Behavior and Theoretical Studies of Pd(II) Allyl Complexes with 2-Phenyl-3H-indoles as Ligands

et al. 2019

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The study of the reactivity of three 2-phenyl-3H-indole ligands of general formulae C8H3N-2-(C6H4-4-R1)-3-NOMe-5-R2 (1) [with R1 = H, R2 = OMe (a); R1 = R2 = H (b) or R1 = Cl, R2 = H (c)] with [Pd(η3-1-R3C3H4)(μ-Cl)]2 (R3 = H or Ph) has allowed us to isolate two sets of new Pd(II)-allyl complexes of general formulae [Pd(η3-1-R3C3H4)(1)Cl] {R3 = H (2) or Ph (3)}. Compounds 2a–2c and 3a–3c were characterized by elemental analyses, mass spectrometry and IR spectroscopy. The crystal structures of 2a, 3a and 3b were also determined by X-ray diffraction. 1H-NMR studies reveal the coexistence of two (for 2a–2c) or three (for 3a–3c) isomeric forms in CD2Cl2 solutions at 182 K. Additional studies on the catalytic activity of mixtures containing [Pd(η3-C3H5)(μ-Cl)]2 and the parent ligand (1a–1c) in the allylic alkylation of (E)-3-phenyl-2-propenyl (cinnamyl) acetate with sodium diethyl 2-methylmalonate as well as the stoichiometric reaction between compounds 3a and 3c with the nucleophile reveal that in both cases the formation of the linear trans- derivative is strongly preferred over the branched product. Computational studies at a DFT level on compound 3a allowed us to compare the relative stability of their isomeric forms present in solution and to explain the regioselectivity of the catalytic and stoichiometric processes.

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Water vs. Organic Solvents: Water‐Controlled Divergent Reactivity of 2‐Substituted Indoles

Hashidoko,

Kitanosono,

Yamashita

et al. 2024

Chemistry An Asian Journal

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Water is not a good solvent for most organic compounds, yet water can offer many benefits to some organic reactions, hence enriching organic chemistry. Herein, the unique divergent reactivity of 2‐substituted indoles with •NO sources is presented. The amount of water solvent was harnessed for a scalable, benign, and expedient synthesis of indolenine oximes, albeit with water’s inability to dissolve the reactants. 2‐Methoxyethyl nitrite, which has been tailored for reactions in water, empowered this protocol by enhancing the product selectivity. We further report on chemoselective transformations of the products that rely on their structural features. Our findings are expected to offer access to an underexplored chemical space. The platform is also applicable to oximinomalonate synthesis. Mechanistic studies revealed the important role of water in the reversal of stability between oxime and nitroso compounds, promoting the proton transfer.

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Cyclopalladation of 3-methoxyimino-2-phenyl-3H-indoles

Cited by 10 publications

References 68 publications

Platinum(II) and palladium(II) complexes with (N,N′) and (C,N,N′)− ligands derived from pyrazole as anticancer and antimalarial agents: Synthesis, characterization and in vitro activities

Platinum(II) and palladium(II) complexes with (N,N′) and (C,N,N′)− ligands derived from pyrazole as anticancer and antimalarial agents: Synthesis, characterization and in vitro activities

Synthesis, Characterization, Solution Behavior and Theoretical Studies of Pd(II) Allyl Complexes with 2-Phenyl-3H-indoles as Ligands

Water vs. Organic Solvents: Water‐Controlled Divergent Reactivity of 2‐Substituted Indoles

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