Palladium(II) and Platinum(II) Deprotonated Diaminocarbene Complexes Based on N-(2-Pyridyl)ureas with Oxadiazole Periphery

Geyl, Kirill K.; Baykova, Svetlana O.; Andoskin, P.; Sharoyko, Vladimir V.; Eliseeva, Anastasiya A.; Baykov, Sergey V.; Semenov, Konstantin N.; Boyarskiy, Vadim P.

doi:10.3390/inorganics10120247

Cited by 6 publications

(7 citation statements)

References 65 publications

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“…For example, Boyarskiy et al reported the successful synthesis of 1,2,4-oxadiazoles substituted by pyridine N -oxides [ 115 ], and the N -oxide functionality was compatible with both “ester” and “acid” protocols. Furthermore, these N -oxides were converted into corresponding N -pyridyl ureas [ 115 , 116 ], which are valuable “masked isocyanates” [ 117 , 118 ] and ligands of metal-based anticancer drugs [ 119 , 120 ]. Krasavin et al continued the exploration of 1,2,4-oxadiazole motif for the design of carbonic anhydrase inhibitors [ 14 , 114 ].…”

Section: Base-induced Cyclodehydration Of O -Acyla...mentioning

confidence: 99%

Room Temperature Synthesis of Bioactive 1,2,4-Oxadiazoles

Baykov

Shetnev

Semenov

et al. 2023

IJMS

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1,2,4-Oxadiazole is an essential motif in drug discovery represented in many experimental, investigational, and marketed drugs. This review covers synthetic methods that allow the conversion of different types of organic compounds into 1,2,4-oxadiazole at ambient temperature and the practical application of the latter approaches for the preparation of pharmaceutically important molecules. The discussed methods are divided into three groups. The first combines two-stage protocols requiring the preliminary preparation of O-acylamidoximes followed by cyclization under the action of organic bases. The advantages of this route are its swiftness, high efficiency of the cyclization process, and uncomplicated work--up. However, it requires the preparation and isolation of O-acylamidoximes as a separate preliminary step. The second route is a one-pot synthesis of 1,2,4-oxadiazoles directly from amidoximes and various carboxyl derivatives or aldehydes in aprotic bipolar solvents (primarily DMSO) in the presence of inorganic bases. This recently proposed pathway proved to be highly efficient in the field of medicinal chemistry. The third group of methods consists of diverse oxidative cyclizations, and these reactions have found modest application in drug design thus far. It is noteworthy that the reviewed methods allow for obtaining 1,2,4-oxadiazoles with thermosensitive functions and expand the prospects of using the oxadiazole core as an amide- or ester-like linker in the design of bioactive compounds.

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Section: Base-induced Cyclodehydration Of O -Acyla...mentioning

confidence: 99%

Room Temperature Synthesis of Bioactive 1,2,4-Oxadiazoles

Baykov

Shetnev

Semenov

et al. 2023

IJMS

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“…Previously, we developed a simple method [70][71][72] for the preparation of N,N-dialkyl-N'-pyridylureas and utilized these compounds as ligands to obtain metal-based anti-cancer agents [73,74] and catalysts. [75,76] Moreover, it has found that such ureas are able to react with N-and O-nucleophiles acted like masked hetaryl isocyanates.…”

Section: Introductionmentioning

confidence: 99%

N‐Pyridylureas as Masked Isocyanates Fort the Late‐Stage Diversification of Pyridine‐N‐Oxides

Baykova,

Baykov,

Geyl

et al. 2024

ChemistrySelect

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A new method for the synthesis of pyridine‐ and quinoline‐N‐oxides containing a ureido or carbamoyl fragment in position 2 has been developed. This method concluded in the oxidation of relatively readily available substituted N,N‐dimethyl‐N′‐(pyridine‐2‐yl)ureas to the corresponding N‐oxides, followed by modification of the dimethylureide moiety. Being heated to 90 °C in the presence of amines in a solution of DMF or chlorobenzene, N‐oxide of N,N‐dimethyl‐N′‐(pyridine‐2‐yl)urea undergoes a transamination reaction without loss of the N‐oxide function. This produces N‐oxides of N‐alkyl/aryl‐N’‐(pyridine‐2‐yl)ureas in 24–99 % yields, (about 30 examples). Values of the NH protons chemical shifts are a good criterion for the selectivity of the reaction. The reaction is also applicable to N‐oxides of ureas substituted in the pyridine ring and to the quinoline congener. N‐Oxides of pyridine/quinoline‐containing carbamates can be similarly prepared by heating N‐oxides of N,N‐dimethyl‐N′‐(pyridine‐2‐yl)/(quinoline‐2‐yl)‐urea in an appropriate alcohol solution at 120 °C.

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“…They effectively catalyze the processes of C-C cross-coupling [4][5][6][7][8], hydrosilylation [9][10][11], and C≡C triple-bond activation [12,13]. Moreover, several compounds are recognized as promising antitumor agents [14,15], probes of mercury(II) ions in solutions [16], and components of OLED devices [17].…”

Section: Introductionmentioning

confidence: 99%

Conformation-Associated C···dz2-PtII Tetrel Bonding: The Case of Cyclometallated Platinum(II) Complex with 4-Cyanopyridyl Urea Ligand

Baykov,

Katlenok,

Baykova

et al. 2024

IJMS

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The nucleophilic addition of 3-(4-cyanopyridin-2-yl)-1,1-dimethylurea (1) to cis-[Pt(CNXyl)2Cl2] (2) gave a new cyclometallated compound 3. It was characterized by NMR spectroscopy (1H, 13C, 195Pt) and high-resolution mass spectrometry, as well as crystallized to obtain two crystalline forms (3 and 3·2MeCN), whose structures were determined by X-ray diffraction. In the crystalline structure of 3, two conformers (3A and 3B) were identified, while the structure 3·2MeCN had only one conformer 3A. The conformers differed by orientation of the N,N-dimethylcarbamoyl moiety relative to the metallacycle plane. In both crystals 3 and 3·2MeCN, the molecules of the Pt(II) complex are associated into supramolecular dimers, either {3A}2 or {3B}2, via stacking interactions between the planes of two metal centers, which are additionally supported by hydrogen bonding. The theoretical consideration, utilizing a number of computational approaches, demonstrates that the C···dz2(Pt) interaction makes a significant contribution in the total stacking forces in the geometrically optimized dimer [3A]2 and reveals the dz2(Pt)→π*(PyCN) charge transfer (CT). The presence of such CT process allowed for marking the C···Pt contact as a new example of a rare studied phenomenon, namely, tetrel bonding, in which the metal site acts as a Lewis base (an acceptor of noncovalent interaction).

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Palladium(II) and Platinum(II) Deprotonated Diaminocarbene Complexes Based on N-(2-Pyridyl)ureas with Oxadiazole Periphery

Cited by 6 publications

References 65 publications

Room Temperature Synthesis of Bioactive 1,2,4-Oxadiazoles

Room Temperature Synthesis of Bioactive 1,2,4-Oxadiazoles

N‐Pyridylureas as Masked Isocyanates Fort the Late‐Stage Diversification of Pyridine‐N‐Oxides

Conformation-Associated C···dz2-PtII Tetrel Bonding: The Case of Cyclometallated Platinum(II) Complex with 4-Cyanopyridyl Urea Ligand

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