Transition metal(ii) complexes of halogenated derivatives of (E)-4-(2-(pyridin-2-ylmethylene)hydrazinyl)quinazoline: structure, antioxidant activity, DNA-binding DNA photocleavage, interaction with albumin andin silicostudies

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(43), P. 16688 - 16705

Published: Jan. 1, 2022

Two novel halogenated (Br- and F-) quinazoline derivatives, namely [(E)-4-(2-((6-bromopyridin-2-yl)methylene)hydrazinyl)quinazoline] (L1) [(E)-4-(2-((3-fluoropyridin-2-yl)methylene)hydrazinyl) quinazoline] (L2), were synthesized characterized. Their interaction with a series of metal(II) ions (= Mn(II), Ni(II), Cu(II), Zn(II) Cd(II)) resulted in the formation six mononuclear complexes characterized by spectroscopic techniques single-crystal X-ray crystallography. The bear formulae [Ni(L1)2](NO3)2 (1), [Zn(L2)2](NO3)(PF6) (2), [Cd(L2)(H2O)(CH3OH)(NO3)](NO3) (3), [Cu(L2)Cl2] (4), [Ni(L2)2](NO3)2 (5) [Mn(L2)(CH3OH)(Cl)2] (6). biological activity compounds was further evaluated vitro regarding their calf-thymus DNA, cleavage ability towards supercoiled circular pBR322 plasmid DNA absence or presence irradiation at various wavelengths (UVA, UVB visible light), affinity to bovine serum albumin scavenge 1,1-diphenyl-picrylhydrazyl 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radicals reduce H2O2. In silico molecular docking calculations employed study behavior albumin.

Language: Английский

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Direct N‐Alkylation of Amines with Alcohols Catalyzed by N‐Heterocyclic Carbene Cobalt‐Pincer Catalyst under Mild Conditions

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(3)

Published: Jan. 11, 2024

Abstract Alcohols are widely available and can be derived from renewable resources. Catalytic alcohol amination for N ‐alky amine synthesis using the borrowing hydrogen strategy is an environmentally benign prominent sustainable method, which produces water as sole byproduct. However, expensive noble metals generally employed this transformation, while nonprecious metal‐based catalysts were also known reaction have attracted considerable attention recently. Herein, efficient ‐alkylation of amines with alcohols base‐metal cobalt reported. This catalyzed by N‐heterocyclic carbene cobalt‐pincer catalyst operates simply under mild conditions. Various aniline substrates functional groups including nitrile, ether, thioether alkene could well tolerated. Moreover, experimental studies DFT calculations performed to illustrate mechanism. Our results suggest that proceeds via a autotransfer

Language: Английский

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NNO Pincer-Supported Pd(II)-Catalyzed Reductive N-Alkylation of Challenging Nitroarenes with Alcohols via Borrowing Hydrogen Strategy

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11161 - 11172

Published: July 31, 2024

A sustainable catalytic synthesis of selective monoalkylated amines from nitroarenes and alcohols by new palladium(II)-NNO pincer-type complexes has been described. Herein, a series Pd(II) [Pd(NNO)PPh

Language: Английский

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Half-sandwich iridium complexes with hydrazone ligands: preparation, structure, and catalytic synthesis of cyanosilylethers under air

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(32), P. 11104 - 11112

Published: Jan. 1, 2023

A series of hydrazone-based N,O-chelate half-sandwich iridium complexes were synthesized through a facile route with good yields. These air- and moisture-stable exhibited excellent catalytic activity in the cyanosilylether synthesis under mild reaction conditions. Under catalysis iridium, various cyanosilylethers different substituents obtained one-pot trimethylsilyl cyanide (TMSCN) carbonyl substrates, to The efficiency, wide substrate range, conditions made this type catalyst have potential for industrial applications. All well characterized by IR, NMR, EA analyses. molecular structure complex 1 was confirmed single-crystal X-ray analysis.

Language: Английский

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

Applied Organometallic Chemistry, Journal Year: 2023, Volume and Issue: 37(10)

Published: Aug. 22, 2023

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

Language: Английский

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Co(II) Acetate‐Assisted Direct Synthesis of Acyl Hydrazones from Acyl Hydrazides under Mild Conditions

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(22)

Published: Oct. 10, 2023

Acyl hydrazones are a class of synthetically important organic compounds that recurrently in high demand for synthesis and use various fields chemistry biology. We report the first Co(II) catalyzed one-component one-pot sustainable acyl only from hydrazides under mild reaction conditions. Traditional contemporary methodologies two components (usually aldehydes/ketones/alcohols/styrene) as coupling partners. Our protocol, on other hand, involves situ generation aldehyde intermediate (detected by gas chromatography) hydrazide, which then undergoes condensation with another molecule same hydrazide pot to yield presence base K2 CO3 low-cost Co(OAc)2 ⋅ 4H2 O catalyst. This method shows good functional group tolerance excellent products. Furthermore, some resulting have been used synthetic precursors explored post-synthetic modifications afford N-heterocyclic compounds. photoswitchable properties few synthesized also using their E/Z isomerization around C=N bond, realized high-pressure liquid chromatography (HPLC) UV-vis spectroscopic studies.

Language: Английский

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Cyclometalated Half-Sandwich Ruthenium Complexes: Preparation, Structure, and Catalytic Synthesis of Phenolic Esters from Aryl Halides without Using External CO under Air

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(44), P. 18198 - 18208

Published: Oct. 23, 2023

A series of cyclometalated C,N-chelate half-sandwich ruthenium complexes based on N-heterocyclic ligands were prepared through a simple route with good yields. These air- and moisture-stable showed excellent catalytic efficiency in phenoxy carbonylation aryl halides phenyl formate derivatives as CO source phenol coupling partner under air. Ester products obtained high yields at room temperature without the need for an inert atmosphere. The activity, broad substrate range, mild reaction conditions made this system potential industrial production. In addition, DFT study has been carried out to elaborate possible mechanism Ru-catalyzed reaction.

Language: Английский

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Cyclometalated half‐sandwich iridium complexes: Synthesis, characterization, and catalytic activity in preparation of esters from halides by using formate as both CO source and coupling partner

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 38(8)

Published: May 30, 2024

A highly efficient carbonylation of aryl halides using half‐sandwich iridium catalysis was developed, providing a new avenue for synthesizing carboxylic ester derivatives and yielding consistently impressive results. These complexes demonstrated remarkable catalytic performance in the coupling reaction phenyl formate as source CO, phenol, starting material presence air possessed good moisture stability properties. Ester products with different substituents were synthesized at low temperatures without need an inert atmosphere, leading to high yields. The broad substrate scope, activity, mild conditions suggest promising industrial applications this system. desired metal 1 – 4 have been well proven by attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR), nuclear magnetic resonance (NMR), elemental analysis (EA). molecular structure cyclometalated 2 3 through X‐ray crystallography. Additionally, possible mechanism Ir‐catalyzed process is further supported density functional theory (DFT) study.

Language: Английский

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Nickel complexes bearing quinoline derived NNS donor ligands as catalytic activators for N‐alkylation of anilines with alcohols

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 12, 2024

Abstract Herein, we have reported a new series of NNS‐donor ligands coordinated Ni(II) complexes and utilized them as catalytic activator to synthesize N ‐alkylated amines 1,2‐disubstituted benzimidazoles. The reaction thiophenol/4‐chlorothiophenol/4‐methylthiophenol/4‐methoxythiophenol with 2‐bromo‐ ‐quinolin‐8‐yl‐acetamide in presence sodium hydroxide ethanol at 80 °C gave [C 9 H 6 N‐NH−C(O)−CH 2 ‐S−Ar] [Ar=C 5 ( L1 ); C 4 Cl‐4 (L2 Me‐4 (L3 ) ‐OMe‐4 (L4 )], respectively. corresponding ‐ L4 Ni(OAc) methanol for 3 hours resulted octahedral nickel [( ‐H) Ni] C1 ), L2 C2 L3 C3 C4 All compounds been characterized by micro spectroscopic analysis. molecular structure – has also determined single crystal X‐ray diffraction data. utility were evaluated the ‐alkylation aniline benzyl alcohols, benzimidazoles synthesis. obtained results indicate that complex showed better activity both alcohols [catalyst loading: 2.0 mol %; Yield up 92 %], derivatives 94 %)]. mechanistic studies suggested works through hydrogen borrowing from alcohol its subsequent utilization situ reduction imine. experimentally observed reactivity patterns found good agreement HOMO‐LUMO energy gaps DFT analysis complexes.

Language: Английский

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Half‐sandwich iridium complexes: Synthesis and catalytic activity in dehydrogenation of alcohols to carboxylic acids

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 38(11)

Published: July 25, 2024

A series of N , ‐chelate half‐sandwich iridium complexes were synthesized by a simple method with good yields. The dehydrogenation aromatic and aliphatic primary alcohols to corresponding carboxylic acids has been successfully achieved the prepared air stable under mild reaction conditions. Carboxylic obtained in high yields open flask condition broad substrates tolerance sensitive functional groups. Such catalyst system showed desirable stability catalytic activity, achievement TOF 372.0 h −1 could be observed an extremely low loading only 0.05 mol%. Furthermore, sustainable reused for minimum five cycles without obviously losing its highlighting potential application industry. Structure 1 3 determined single‐crystal X‐ray analysis.

Language: Английский

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