ChemInform Abstract: Ruthenium-Catalyzed Rearrangements of Azobenzenes. Part 1. The Preparation of l-Phenylbenzimidazoles from Azobenzene Derivates and Tertiary Amines Catalyzed by Ruthenium Complexes.

1986 ◽  
Vol 17 (11) ◽  
Author(s):  
A. SPENCER
Keyword(s):  
Ruthenium Complexes ◽  
Tertiary Amines

Amide versus amine ligand paradigm in the direct amination of alcohols with Ru-PNP complexes

2018 ◽  
Vol 8 (15) ◽  
pp. 3969-3976 ◽  
Author(s):  
Dennis Pingen ◽  
Jong-Hoo Choi ◽  
Henry Allen ◽  
George Murray ◽  
Prasad Ganji ◽  
...  
Keyword(s):  
Ruthenium Complexes ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Direct Amination ◽  
Amine Ligand ◽  
Amide Versus

Ruthenium complexes of PNP-ligands bearing secondary amines were found to be inactive in the alcohol amination with NH3, while all complexes of homologous ligands bearing tertiary amines gave active catalysts!

Mechanistic Insights into Fe Catalyzed α-C-H Oxidations of Tertiary Amines

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert
Keyword(s):  
Free Radical ◽  
Catalytic Mechanism ◽  
Catalyst System ◽  
Oxidation Products ◽  
Tertiary Amines ◽  
Catalyst Activation ◽  
Rate Determining Step ◽  
Fe Catalyst ◽  
Ligand Coordination ◽  
Rate Kinetics

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>

Heterogeneous Bimetallic Pt-Sn/γ-Al2O3 Catalyzed N-Alkylation of Amines: Ef-ficient Synthesis of Secondary and Tertiary Amines

2013 ◽  
Vol 33 (4) ◽  
pp. 717-722 ◽  
Author(s):  
Wei HE ◽  
Songbo HE ◽  
Chenglin SUN ◽  
Kaikai WU ◽  
Liandi WANG ◽  
...  
Keyword(s):  
Tertiary Amines

Solid Supported Ruthenium Complexes for Olefin Metathesis

2013 ◽  
Vol 17 (22) ◽  
pp. 2592-2608 ◽  
Author(s):  
Fatma Hamad ◽  
Cheng Kai ◽  
Yuan Cai ◽  
Yu Xie ◽  
Yin Lu ◽  
...  
Keyword(s):  
Olefin Metathesis ◽  
Ruthenium Complexes

Synthesis and Biological Evaluations of Organoruthenium Scaffolds: A Comprehensive Update

2018 ◽  
Vol 15 (2) ◽  
pp. 179-207
Author(s):  
Ashaparna Mondal ◽  
Priyankar Paira
Keyword(s):  
Singlet Oxygen ◽  
Anticancer Agents ◽  
Ruthenium Complexes ◽  
Chemotherapeutic Agents ◽  
Quantum Yields ◽  
Ros Generation ◽  
Standard Drug ◽  
Cellular Environment ◽  
Theranostic Agents

Background: Currently ruthenium complexes are immerging as effective anticancer agents due to their less toxicity, better antiproliferative and antimetastatic activity, better stability in cellular environment and most importantly variable oxidation and co-ordination states of ruthenium allows binding this molecule with a variety of ligands. So in past few years researchers have shifted their interest towards organoruthenium complexes having good fluorescent profile that may be applicable for cancer theranostics. Nowadays, photodynamic therapy has become more acceptable because of its easy and effective approach towards killing cancer cells. Objective: Objective of this review article is to shed light on synthesis, characterization, stability and fluorescence studies of various ruthenium [Ru(II) and Ru(III)] complexes and different bioactivity studies conducted with the synthesized compounds to test their candidacy as potent chemotherapeutic agents. Methods: Various heterocyclic ligands containing N,O and S as heteroatom mainly were prepared and subjected to complexation with ruthenium-p-cymene moiety. In most cases [Ru(η6-p-cymene)(µ-Cl)Cl]2 was used as ruthenium precursor and the reactions were conducted in various alcohol medium such as methanol, ethanol or propanol. The synthesized complexes were characterized by 1H NMR and 13C NMR spectroscopy, GC-MS, ESI-MS, elemental analysis and single crystal X-ray crystallography methods. Fluorescence study and stability study were conducted accordingly using water, PBS buffer or DMSO. Stable compounds were considered for cell viability studies. To study the efficacy of the compounds in ROS generation as photosensitizers, in few cases, singlet oxygen quantum yields in presence of light were calculated. Suitable compounds were selected for in vitro & in vivo antiproliferative, anti-invasive activity studies. Result: Many newly synthesized compounds were found to have less IC50 compared to a standard drug cysplatin. Those compounds were also stable preferably in physiological conditions. Good fluorescence profile and ROS generation ability were observed for few compounds. Conclusion: Numerous ruthenium complexes were developed which can be used as cancer theranostic agents. Few molecules were synthesized as photosensitizers which were supposed to generate reactive singlet oxygen species in targeted cellular environment in presence of a particular type of light and thereby ceasing cancer cell growth.

New Cathepsin D Inhibitor Library Utilizing Hydroxyethyl Isosteres with Cyclic Tertiary Amines

2012 ◽  
Vol 8 (6) ◽  
pp. 1146-1154
Author(s):  
Rose M. McConnell ◽  
Kalyani Inapudi ◽  
Naveen Kadasala ◽  
Karthika Yarlagadda ◽  
Priya Velusamy ◽  
...  
Keyword(s):  
Cathepsin D ◽  
Tertiary Amines

Reaction of arylmethylenemalonaldehydes with some nucleophiles

1987 ◽  
Vol 52 (11) ◽  
pp. 2699-2709 ◽  
Author(s):  
Dalimil Dvořák ◽  
Zdeněk Arnold
Keyword(s):  
Inorganic Anions ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Primary And Secondary Amines ◽  
Dipolar Structure

Reaction of arylmethylenemalonaldehydes with tributylphosphine and tertiary amines affords compounds of dipolar structure whereas reaction with primary and secondary amines leads to 1,4-addition products. Salts of nucleophilic inorganic anions add to arylmethylenemalonaldehydes under formation of salts of substituted malonaldehydes.

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

Light activation of cyclometalated ruthenium complexes drives towards caspase 3 dependent apoptosis in gastric cancer cells

2020 ◽  
Vol 208 ◽  
pp. 111080 ◽  
Author(s):  
Jorge Andrés Solís-Ruiz ◽  
Anaïs Barthe ◽  
Gilles Riegel ◽  
Rafael Omar Saavedra-Díaz ◽  
Christian Gaiddon ◽  
...  
Keyword(s):  
Gastric Cancer ◽  
Cancer Cells ◽  
Caspase 3 ◽  
Ruthenium Complexes ◽  
Light Activation ◽  
Gastric Cancer Cells
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