41756-81-4Relevant academic research and scientific papers
Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition-Metal Catalysts
Oestreich, Martin,Seliger, Jan
supporting information, p. 247 - 251 (2020/10/29)
A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.
Pyridine-pyridine-imidazoline-containing asymmetric NNN' pincerlike ruthenium compound and preparation method thereof
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Paragraph 0017, (2019/07/16)
The invention discloses a pyridine-pyridine-imidazoline-containing asymmetric NNN' pincerlike ruthenium compound and a preparation method thereof. A general formula of the pyridine-pyridine-imidazoline-containing asymmetric NNN' pincerlike ruthenium compound is shown in the description, wherein R1 is C1-C15 alkyl and aryl, and R2 is aryl. A synthesis method of the pincerlike ruthenium compound comprises the following steps: 2,2-bipyridyl is oxidized by hydrogen peroxide, nitrileated, and hydrolyzed to obtain 2,2-bipyridyl-6-carboxylic acid, the 2,2-bipyridyl-6-carboxylic acid is chlorinated, aminated, re-chlorinated and cyclized to obtain a ligand, and the ligand and RuCl2(PPh3)3 are refluxed in toluene to obtain the pyridine-pyridine-imidazoline-containing asymmetric NNN' pincerlike ruthenium compound. The invention provides a simple and convenient method for synthesizing the asymmetric pincerlike ruthenium compound by using inexpensive and readily available 2,2-bipyridyl as a starting material.
Ru(II)/N-N/PPh3 complexes as potential anticancer agents against MDA-MB-231 cancer cells (N-N?=?diimine or diamine)
Ribeiro, Gabriel H.,Colina-Vegas, Legna,Clavijo, Juan C.T.,Ellena, Javier,Cominetti, Marcia R.,Batista, Alzir A.
, p. 70 - 83 (2019/01/26)
The rational design of anticancer agents that acts in specific biological targets is one of the most effective strategies for developing chemotherapeutic agents. Aiming at obtaining new ruthenium (II) compounds with good cytotoxicity against tumor cells, a series of new complexes of general formula [RuCl(PPh3)(Hdpa)(N–N)]Cl [PPh3 = triphenylphosphine, N-N = 2,2′-dipyridylamine (Hdpa) (1), 1,2-diaminoethane (en) (2), 2,2′-bipyridine (bipy) (3), 5,5′-dimethyl-2,2′-bipyridine (dmbipy) (4), 1,10-phenanthroline (phen) (5) and 4,7-diphenyl-1,10-phenanthroline (dphphen) (6)] were synthesized. The complexes were characterized by elemental analysis and spectroscopic techniques (IR, UV/Visible, and 1D and 2D NMR) and three of their X-ray structures were determined: [RuCl(PPh3)(Hdpa)2]Cl, [RuCl(PPh3)(Hdpa)(en)]Cl and [RuCl(PPh3)(Hdpa)(dmbipy)]Cl. All the complexes are more cytotoxic against the cancer cell line than against the non-tumor cell line, highlighting complexes 1 and 5, which have an index selectivity of 18 and 15, respectively. The binding constants of compounds 1–6 with human serum albumin (HSA) were determined by tryptophan fluorescence quenching, indicating moderate to strong interactions. The binding mode of the complexes to calf thymus (CT) DNA was explored by several techniques, which reveal that only the dphphen compound 6 causes distortions in the secondary and tertiary structures of DNA. The studies demonstrated that the nature of the N–N co-ligand and the presence of the PPh3 and Hdpa ligands are features that can influence the binding affinity of the complexes by the biomolecules and in the cytotoxic activity of the complexes. Overall, the complexes with diimine co-ligand are much more cytotoxic than compound 2 with the aliphatic diamine.
Heteroleptic tris-chelate ruthenium(II) complexes of N,N-disubstituted-N′-acylthioureas: Synthesis, structural studies, cytotoxic activity and confocal microscopy studies
Barolli, Jo?o P.,Maia, Pedro I.S.,Colina-Vegas, Legna,Moreira, Jane,Plutin, Ana M.,Mocelo, Raúl,Deflon, Victor M.,Cominetti, Marcia R.,Camargo-Mathias, Maria I.,Batista, Alzir A.
, p. 33 - 41 (2017/02/13)
Ruthenium complexes have been assessed as anti-tumor agents against cancer cells. In this project, new heteroleptic ruthenium(II) complexes with general formulae [Ru(L)(bipy)(dppb)](PF6) (where L?=?N,N-disubstituted-N′-acylthiourea, bipy?=?2,2′-bipyridine and dppb?=?1,4-bis(diphenylphosphino)butane) were synthesized and characterized by elemental analysis, IR and NMR (1H and31P{1H}) spectroscopies, molar conductivity measurements and single crystal X-ray diffractometry. The IR and NMR data suggest the coordination of the ligands to the Ru(II) metal center through the thiocarbonyl and carbonyl groups. The structures of the new complexes were further studied by X-ray crystallography, which confirmed the coordination of the ligands with the metal through the sulfur and oxygen atoms, leading to the formation of distorted octahedral complexes. The N,N-disubstituted-N′-acylthioureas and their complexes were screened with respect to their in vitro cytotoxicity. All compounds exhibited considerable antiproliferative activity against MCF-7 (human breast tumor cells ATCC HTB-26), DU-145 (human prostate tumor cells ATCC HTB-26), and relatively low toxicity against fibroblast L929 cells (health cell line from mouse ATCC CCL-1). A preliminary study regarding the mechanism of action of these compounds by confocal microscopy shows alterations of the actin filaments leading to modifications in cytoskeletal supporting the cell death and that the cell nucleus is not main target of these complexes.
Ruthenium complexes of diphenylphosphino derivatives of carboxylic amides: Synthesis and characterization of bidentate P,N- and P,O-chelate ligands and their reactivity towards [RuCl2(PPh3)3]
Gericke, Robert,Wagler, J?rg
, p. 134 - 141 (2016/12/06)
The carboxylic amides N-methylbenzamide (HLa), phthalimidine (HLb) and pyridine-2-one (HLc) were diphenylphosphino-functionalized (with ClPPh2and a base, n-BuLi for HLa, triethylamine for HLb and HLc) to yield the N-PPh2derivatives o
Ru(II)/clotrimazole/diphenylphosphine/bipyridine complexes: Interaction with DNA, BSA and biological potential against tumor cell lines and Mycobacterium tuberculosis
Colina-Vegas, Legna,Dutra, Jocely Lucena,Villarreal, Wilmer,de A. Neto, Jo?o Honorato,Cominetti, Marcia Regina,Pavan, Fernando,Navarro, Maribel,Batista, Alzir A.
, p. 135 - 145 (2016/11/12)
Three ruthenium complexes [RuCl(CTZ)(bipy)(P-P)]PF6 [P-P?=?1,2-bis(diphenylphosphino)ethane (dppe-1), 1,4-bis(diphenylphosphino)butane (dppb-2) and 1,1′-bis(diphenylphosphino)ferrocene (dppf-3), bipy?=?2,2′-bipiridine and clotrimazole (CTZ) 1-[(2-chlorophenyl)diphenylmethyl]-1H-imidazole] were synthesized. These complexes were characterized by a combination of elemental analysis, molar conductivity, infrared and UV–vis spectroscopy, 1H, 13C{1H} and 31P{1H} nuclear magnetic resonance techniques, cyclic voltammetry and mass spectroscopy. Bovine serum albumin binding constants, which were in the range of 1.30–36.00?×?104?M??1, and thermodynamic parameters suggest spontaneous interactions with this protein by electrostatic forces due to the positive charge of the complexes. DNA interactions studied by spectroscopic titration, viscosity measurements, gel electrophoresis, circular dichroism, ethidium bromide displacement and reactions with guanosine and guanosine monophosphate indicated the DNA binding affinity primarily through non-covalent interactions. All complexes 1–3 were tested against the human carcinoma cell lines MCF-7 (breast), A549 (lung) and DU-145 (prostate) presenting promising IC50 values, between 0.50 and 14.00?μM, in some cases lower than the IC50 for the reference drug (cisplatin). The antimicrobial activity assays of the complexes provided evidence that they are potential agents against mycobacterial infections, specifically against Mycobacterium tuberculosis H37Rv.
New, highly efficient, simple, safe, and scalable synthesis of [(Ph 3P)3Ru(CO)(H)2]
Samouei, Hamidreza,Grushin, Vladimir V.
supporting information, p. 4440 - 4443 (2013/09/02)
A new method has been developed to prepare [(Ph3P) 3Ru(CO)(H)2] (1), an important homogeneous catalyst, directly from RuCl3·xH2O. Unlike previously reported procedures to make 1, the new method does not utilize toxic and hazardous materials such as formaldehyde and benzene and requires only a small excess of PPh3, while furnishing analytically and spectroscopically pure 1 in unprecedented >95% yield. The solvent (EtOH) is used in small quantities, thereby enabling scalability, as has been demonstrated by preparing >17 g of pure 1 in one batch.
Thiosemicarbazonates of ruthenium(II): Crystal structures of [Bis(triphenylphosphine)][bis(N-phenyl-pyridine-2-carbaldehyde thiosemicarbazonato)]ruthenium(II) and [Bis(diphenylphosphino)butane] [bis(salicylaldehyde thiosemicarbazonato)]ruthenium(II)
Lobana, Tarlok S.,Bawa, Gagandeep,Butcher, Ray J.,Liu, Chen W.
, p. 355 - 360 (2009/05/09)
Reaction of RuCl2(PPh3)3 with N-Phenyl-pyridine-2-carbaldehyde thiosemicarbazone (C5H 4N-C2(H)=N3-N2H-C 1(=S)-N1HC6H5, Hpyt
Electron exchange involving a sulfur-stabilized ruthenium radical cation
Shaw, Anthony P.,Ryland, Bradford L.,Norton, Jack R.,Buccella, Daniela,Moscatelli, Alberto
, p. 5805 - 5812 (2008/10/09)
Half-sandwich Ru(II) amine, thiol, and thiolate complexes were prepared and characterized by X-ray crystallography. The thiol and amine complexes react slowly with acetonitrile to give free thiol or amine and the acetonitrile complex. With the thiol complex, the reaction is dissociative. The thiolate complex has been oxidized to its Ru(III) radical cation and the solution EPR spectrum of that radical cation recorded. Cobaltocene reduces the thiol complex to the thiolate complex. The 1H and 31P NMR signals of the thiolate complex in acetonitrile become very broad whenever the thiolate and thiol complexes are present simultaneously. The line broadening is primarily due to electron exchange between the thiolate complex and its radical cation; the latter is generated by an unfavorable redox equilibrium between the thiol and thiolate complexes. Pyramidal inversion of sulfur in the thiol complex is fast at room temperature but slow at lower temperatures; major and minor conformers of the thiol complex were observed by 31P NMR at -98°C in CD 2Cl2.
Thiosemicarbazonates of ruthenium(II): Crystal structures of [bis(diphenylphosphino)butane][bis(pyridine-2-carbaldehydethiosemicarbazonato)] ruthenium(II) and [bis(triphenylphosphine)][bis(benzaldehydethiosemicarbazonato)] ruthenium(II)
Lobana, Tarlok S.,Bawa, Gagandeep,Butcher, Ray J.,Liaw, Ben-Jie,Liu, Chen W.
, p. 2897 - 2903 (2008/10/09)
The reaction of Ru2Cl4(dppb)3 {dppb = Ph2P-(CH2)4-PPh2} with pyridine-2-carbaldehyde thiosemicarbazone {C5H4N{single bond}C(H){double bond, long}N3{single bond}N2H{single bond}C({double bond, long}S)NH2, Hpytsc}, and that of RuCl2(PPh3)3 with benzaldehyde thiosemicarbazone {C6H5{single bond}C(H){double bond, long}N3{single bond}N2H{single bond}C({double bond, long}S){single bond}NH2, Hbtsc}, in the presence of Et3N base led to loss of the -N2H- proton in each case, and yielded [Ru(pytsc)2(dppb)] (1) and [Ru(btsc)2(Ph3P)2] (2), respectively. The complexes are characterized with the help of analytical data, IR, NMR (1H, 13C, 31P) and single crystal X-ray study. In both compounds 1 and 2, the thiosemicarbazone ligands coordinate to Ru(II) via the hydrazinic nitrogen (N2) and sulfur atoms forming four membered rings, and the pyridyl group is pendant in 1. The geometry is distorted octahedral with cis:cis:trans P, P:N, N:S, S dispositions of donor atoms. Proton NMR confirmed loss of the -N2H- proton in both compounds, and the 31P NMR spectra reveal the presence of equivalent phosphorus atoms in both the compounds. Compound 1 represents the first example of a Ru(II)-thiosemicarbazone complex with a chelating diphosphine and it reveals the stability of a seven membered P,P-chelate ring in the presence of a potentially tridentate pytsc- ligand.
