Concise access to perimidines by palladium (II) complexes via acceptorless dehydrogenative coupling of alcohols

Selvan, Clinton Savarimuthu; Ramesh, Rengan; Małecki, Jan Grzegorz

doi:10.1002/aoc.6708

Cited by 7 publications

(3 citation statements)

References 31 publications

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“…The biphenyl-4-benzhydrazone ligands were prepared by condensation reactions of biphenyl-4 carboxaldehyde with benzhydrazide derivatives at ambient conditions by following the reported procedure . Ruthenium(II) arene precursors were reacted with the prepared ligands in a 1:2 equivalent ratio and stirred in toluene/Et 3 N for 6 h at room temperature.…”

Section: Resultsmentioning

confidence: 99%

Impact of Biphenyl Benzhydrazone-Incorporated Arene Ru(II) Complexes on Cytotoxicity and the Cancer Cell Death Mechanism

et al. 2022

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The biological efficacy of arene ruthenium complexes is currently of great interest due to the significance of arene moieties, chelates, and metal centers in defining and controlling their anticancer activity. The synthesis of six new arene ruthenium(II) complexes containing biphenyl benzhydrazone ligands of general composition [(η6-benzene)Ru(L)Cl] (1–3) and [(η6-p-cymene)Ru(L)Cl] (4–6, L = biphenyl benzhydrazones), and their antiproliferative properties are described in this study. The complexes have been successfully synthesized and thoroughly characterized by elemental analysis and spectral methods such as Fourier transform infrared (FT-IR), UV–vis, NMR, and high-resolution mass spectrometry (HR-MS) techniques. The coordination of azomethine nitrogen and imidolate oxygen of the hydrazone ligand to the ruthenium metal and the presence of a pseudo-octahedral geometry around the ruthenium ion were confirmed by the single-crystal X-ray diffraction (XRD) technique. Further, in vitro cytotoxicity of all of the complexes was evaluated against cancerous A549 (lung cancer), MDA-MB-231 (breast cancer), and HEPG2 (liver cancer) and noncancerous HEK-293 (human kidney) cells and was found to be good with low IC50 values compared to the standard drug cisplatin. In particular, complex 5 exhibits potential cytotoxicity against all of the cancer cells among the synthesized complexes, and this may be attributed to the hydrophobic nature of the p-cymene moiety as well as the substituent effect of the ligand. In addition, staining studies such as AO–EB and Hoechst 33342 ascertain that the complex induces the apoptosis mechanism in cancer cells. Furthermore, reactive oxygen species (ROS) and mitochondrial membrane potential (MMP) confirm apoptosis in cancer cells via the mitochondrial pathway. Additionally, the quantification of apoptosis and ROS have been established by flow cytometry and the plate reader assay, respectively. It is worth noting that the present ruthenium complexes have significant cytotoxicity, raising the prospect of promoting potential ruthenium-based anticancer drugs over platinum drugs.

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Section: Resultsmentioning

confidence: 99%

Impact of Biphenyl Benzhydrazone-Incorporated Arene Ru(II) Complexes on Cytotoxicity and the Cancer Cell Death Mechanism

et al. 2022

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“…In addition, coupling reactions of phenol or tert-butyl alcohol with thiosemicarbazide did not proceed, indicating that the presence of methylene hydrogen is inevitable for the dehydrogenative catalytic pathway. [28,29] A plausible pathway for generating TSCs (Scheme 4) was deduced from the results of control test and previous research report. [26] Benzyl alcohol 1 a was converted into its potassium salt I by reaction with potassium tert-butoxide and then oxidized in air forming the potassium benzyloxy hydroperoxide intermeditae III.…”

Section: Resultsmentioning

confidence: 93%

“…This indicated the base mediated conversion of benzyl alcohol to benzaldehyde 1 a′ during the course of the reaction (Scheme 3). In addition, coupling reactions of phenol or tert‐butyl alcohol with thiosemicarbazide did not proceed, indicating that the presence of methylene hydrogen is inevitable for the dehydrogenative catalytic pathway [28,29] …”

Section: Resultsmentioning

confidence: 99%

Transition Metal Catalyst Free and Single‐Step Synthesis of Significant Thiosemicarbazones via Oxidative Coupling Strategy

Dharani,

Nithya,

Indumathy

et al. 2023

ChemistrySelect

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The efficacy and selectivity of the transition metal‐free catalysis have been emphasized in constructing thiosemicarbazone derivatives from the dehydrogenative coupling of alcohols and thiosemicarbazides under aerobic conditions. A broad spectrum of thiosemicarbazones was obtained in good‐to‐excellent yields up to 90 %, with water as the only by‐product. The catalytic synthesis worked in an atom‐economical fashion in the absence of any oxidant with only 1 mmol of the base loading per mmol of the substrates. Further, the impact of different temperatures, solvents, bases, and base loading of the coupling reaction has been explored. A probable pathway that involves the generation of an aldehyde intermediate to thiosemicarbazones, which releases only water has been proposed.

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N‐alkylation of benzamides/sulfonamides using alcohols via borrowing hydrogen approach by well‐defined Pd (II) pincer complexes

Anandaraj,

Ramesh

2023

Applied Organom Chemis

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The development of green, sustainable, and atom‐economical procedure for the construction of amides via C‐N bond formation is a high priority in synthetic organic community. In this research article, we demonstrate a simple and an efficient catalytic protocol for N‐alkylation of benzamides/sulfonamides using aromatic primary alcohols as coupling partners through borrowing hydrogen (BH) strategy by employing newly constructed palladium (II) O^N^O pincer complexes. All the palladium complexes are characterized by analytical and spectral methods (FT‐IR, NMR, and HRMS). Further, the solid‐state molecular structures of the complexes have been well authenticated by single‐crystal XRD studies. The present N‐alkylation protocol is facile, worked in low catalyst loading (0.5 mol%), and furnishes the desired N‐alkyl amides with excellent yields up to 92%. In this methodology, the reaction proceeds via the formation of intermediates such as aldehyde and (E)‐N‐benzylidenebenzamide with a release of water as ecological by‐product. The control experiments and plausible mechanistic investigations suggested that the coupling reaction was initially proceeds via dehydrogenation of alcohol and generate the alkylated products through hydrogen auto‐transfer. A large‐scale synthesis of N‐(4‐methoxybenzyl)benzamide proves the effectiveness of the Pd (II) pincer catalysts.

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Concise access to perimidines by palladium (II) complexes via acceptorless dehydrogenative coupling of alcohols

Cited by 7 publications

References 31 publications

Impact of Biphenyl Benzhydrazone-Incorporated Arene Ru(II) Complexes on Cytotoxicity and the Cancer Cell Death Mechanism

Impact of Biphenyl Benzhydrazone-Incorporated Arene Ru(II) Complexes on Cytotoxicity and the Cancer Cell Death Mechanism

Transition Metal Catalyst Free and Single‐Step Synthesis of Significant Thiosemicarbazones via Oxidative Coupling Strategy

N‐alkylation of benzamides/sulfonamides using alcohols via borrowing hydrogen approach by well‐defined Pd (II) pincer complexes

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