scholarly journals Ancillary ligand electro-activity effects towards phenyl acetylene homocoupling reaction by a nickel(ii) complex of a non-innocent O-amino phenol ligand: a mechanistic insight

RSC Advances ◽  
2020 ◽  
Vol 10 (41) ◽  
pp. 24176-24189
Author(s):  
Mina Nasibipour ◽  
Elham Safaei ◽  
Marziyeh Sadat Masoumpour ◽  
Andrzej Wojtczak
Keyword(s):  
Ancillary Ligand ◽  
Phenyl Acetylene ◽  
Mechanistic Insight ◽  
Amino Phenol ◽  
Homocoupling Reaction

A new Ni(ii) complex, was synthesized from the reaction of a non-innocent o-aminophenol ligand, and Ni(OAc)2.

Electron microscopy and diffraction of crystalline dendrimers and macrocycles

1993 ◽  
Vol 51 ◽  
pp. 1218-1219
Author(s):  
C. J. Buchko ◽  
P. M. Wilson ◽  
Z. Xu ◽  
J. Zhang ◽  
S. Lee ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Liquid Crystalline ◽  
Structural Information ◽  
High Resolution Electron Microscopy ◽  
Scanning Calorimetry ◽  
Tertiary Butyl ◽  
Phenyl Acetylene ◽  
Selected Area Electron Diffraction ◽  
Liquid Crystalline Phases ◽  
Resolution Electron

The synthesis of well-defined organic molecules with unique geometries opens new opportunities for understanding and controlling the organization of condensed matter. Here, we study dendrimers and macrocycles which are synthesized from rigid phenyl-acetylene spacer units, Both units are solubilized by the presence of tertiary butyl groups located at the periphery of the molecule. These hydrocarbon materials form crystalline and liquid crystalline phases which have been studied by differential scanning calorimetry, hot stage optical microscopy, and wide-angle x-ray scattering (WAXS).The precisely defined architecture of these molecules makes it possible to investigate systematic variations in chemical architecture on the nature of microstructural organization. Here we report on the transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high resolution electron microscopy (HREM) studies of crystalline thin films formed by deposition of these materials onto carbon substrates from dilute solution. Electron microscopy is very attractive for gaining structural information on new molecules due to the scarcity of material to grow single crystals suitable for conventional crystallography.

Arylation of enelactams using TIPSOTf: reaction scope and mechanistic insight

2021 ◽  
Author(s):  
Tomasz J. Idzik ◽  
Zofia M. Myk ◽  
Łukasz Struk ◽  
Magdalena Perużyńska ◽  
Gabriela Maciejewska ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Multinuclear Nmr ◽  
Mechanistic Insight ◽  
Nmr Study ◽  
Wide Range

Triisopropylsilyltrifluoromethanesulfonate can be effectively used for the arylation of a wide range of enelactams. The multinuclear NMR study provided deep insights into the reaction mechanism.

Imine as a Linchpin Approach for Distal C(sp2)–H Functionalization

2020 ◽  
Author(s):  
Sukdev Bag ◽  
Sadhan Jana ◽  
Sukumar Pradhan ◽  
Suman Bhowmick ◽  
Nupur Goswami ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Bond Activation ◽  
Bond Formation ◽  
Ancillary Ligand ◽  
Significant Challenge ◽  
Site Selectivity ◽  
Directing Group ◽  
Covalently Linked ◽  
Complex Organic ◽  
Post Functionalization

<p>Despite the widespread applications of C–H functionalization, controlling site selectivity remains a significant challenge. Covalently attached directing group (DG) served as an ancillary ligand to ensure proximal <i>ortho</i>-, distal <i>meta</i>- and <i>para</i>-C-H functionalization over the last two decades. These covalently linked DGs necessitate two extra steps for a single C–H functionalization: introduction of DG prior to C–H activation and removal of DG post-functionalization. We introduce here a transient directing group for distal C(<i>sp<sup>2</sup></i>)-H functionalization <i>via</i> reversible imine formation. By overruling facile proximal C-H bond activation by imine-<i>N</i> atom, a suitably designed pyrimidine-based transient directing group (TDG) successfully delivered selective distal C-C bond formation. Application of this transient directing group strategy for streamlining the synthesis of complex organic molecules without any necessary pre-functionalization at the distal position has been explored.</p>

New Mechanistic Insight on the PIM-1 Kinase Inhibitor AZD1208 Using Multidrug Resistant Human Erythroleukemia Cell Lines and Molecular Docking Simulations

2019 ◽  
Vol 19 (11) ◽  
pp. 914-926 ◽  
Author(s):  
Maiara Bernardes Marques ◽  
Michael González-Durruthy ◽  
Bruna Félix da Silva Nornberg ◽  
Bruno Rodrigues Oliveira ◽  
Daniela Volcan Almeida ◽  
...  
Keyword(s):  
Molecular Docking ◽  
Binding Site ◽  
Cell Lines ◽  
Chemotherapeutic Agents ◽  
Atp Binding ◽  
Human Leukemia ◽  
Atp Binding Site ◽  
Mechanistic Insight ◽  
Multiple Drugs

Background:PIM-1 is a kinase which has been related to the oncogenic processes like cell survival, proliferation, and multidrug resistance (MDR). This kinase is known for its ability to phosphorylate the main extrusion pump (ABCB1) related to the MDR phenotype.Objective:In the present work, we tested a new mechanistic insight on the AZD1208 (PIM-1 specific inhibitor) under interaction with chemotherapy agents such as Daunorubicin (DNR) and Vincristine (VCR).Materials and Methods:In order to verify a potential cytotoxic effect based on pharmacological synergism, two MDR cell lines were used: Lucena (resistant to VCR) and FEPS (resistant to DNR), both derived from the K562 non-MDR cell line, by MTT analyses. The activity of Pgp was ascertained by measuring accumulation and the directional flux of Rh123. Furthermore, we performed a molecular docking simulation to delve into the molecular mechanism of PIM-1 alone, and combined with chemotherapeutic agents (VCR and DNR).Results:Our in vitro results have shown that AZD1208 alone decreases cell viability of MDR cells. However, co-exposure of AZD1208 and DNR or VCR reverses this effect. When we analyzed the ABCB1 activity AZD1208 alone was not able to affect the pump extrusion. Differently, co-exposure of AZD1208 and DNR or VCR impaired ABCB1 activity, which could be explained by compensatory expression of abcb1 or other extrusion pumps not analyzed here. Docking analysis showed that AZD1208 is capable of performing hydrophobic interactions with PIM-1 ATP- binding-site residues with stronger interaction-based negative free energy (FEB, kcal/mol) than the ATP itself, mimicking an ATP-competitive inhibitory pattern of interaction. On the same way, VCR and DNR may theoretically interact at the same biophysical environment of AZD1208 and also compete with ATP by the PIM-1 active site. These evidences suggest that AZD1208 may induce pharmacodynamic interaction with VCR and DNR, weakening its cytotoxic potential in the ATP-binding site from PIM-1 observed in the in vitro experiments.Conclusion:Finally, the current results could have a pre-clinical relevance potential in the rational polypharmacology strategies to prevent multiple-drugs resistance in human leukemia cancer therapy.

Piperazine as an Inexpensive and Efficient Ligand for Pd-Catalyzed Homocoupling Reactions to Synthesize Bipyridines and Their Analogues

2019 ◽  
Vol 16 (1) ◽  
pp. 173-180
Author(s):  
Mingwei Chen ◽  
Jinyu Hu ◽  
Xiaoli Tang ◽  
Qiming Zhu
Keyword(s):  
Transition Metal ◽  
Oxidation State ◽  
Coupling Reaction ◽  
Aryl Halides ◽  
Metal Species ◽  
Good Substrate ◽  
Active Metal ◽  
Homocoupling Reaction ◽  
Catalytic Cycles ◽  
Reductive Homocoupling

Aim and Objective: The synthesis of bipyridines, especially 2, 2’-bipyridines, remains challenging because the catalytic cycle can be inhibited due to coordination of bipyridine to transition metal. Thus, the development of efficient methods for the synthesis of bipyridines is highly desirable. In the present work, we presented a promising approach for preparation of bipyridines via a Pd-catalyzed reductive homocoupling reaction with simple piperazine as a ligand. Materials and Methods: Simple and inexpensive piperazine was used as a ligand for Pd-catalyzed homocoupling reaction. The combination of Pd(OAc)2 and piperazine in dimethylformamide (DMF) was observed to form an excellent catalyst and efficiently catalyzed the homocoupling of azaarenyl halides, in which DMF was used as the solvent without excess reductants although stoichiometric reductant was generally required to generate the low-oxidation-state active metal species in the catalytic cycles. </P><P> Results: In this case, good to excellent yields of bipyridines and their (hetero) aromatic analogues were obtained in the presence of 2.5 mol% of Pd(OAc)2 and 5 mol% of piperazine, using K3PO4 as a base in DMF at 140°C. Conclusion: According to the results, piperazine as an inexpensive and efficient ligand was used in the Pd(OAc)2-catalyzed homocoupling reaction of heteroaryl and aryl halides. The coupling reaction was operationally simple and displayed good substrate compatibility.

scholarly journals Mechanistic insight into B(C6F5)3 catalyzed imine reduction with PhSiH3 under stoichiometric water conditions

RSC Advances ◽  
2021 ◽  
Vol 11 (34) ◽  
pp. 20961-20969
Author(s):  
Yunqing He ◽  
Wanli Nie ◽  
Ying Xue ◽  
Qishan Hu
Keyword(s):  
Mechanistic Insight ◽  
Excess Water ◽  
Water Conditions ◽  
Imine Reduction ◽  
Water Amount ◽  
Insight Into

Hydrosilylation or amination products? It depends on water amount and nucleophiles like excess water or produced/added amines.

scholarly journals Studies on the Modification of Commercial Bisphenol-A-Based Epoxy Resin Using Different Multifunctional Epoxy Systems

2021 ◽  
Vol 2 (2) ◽  
pp. 419-430
Author(s):  
Ankur Bajpai ◽  
James R. Davidson ◽  
Colin Robert
Keyword(s):  
Mechanical Properties ◽  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Bisphenol A ◽  
Epoxy Resin ◽  
Tensile Fracture ◽  
Chemical Structures ◽  
Amino Phenol ◽  
Epoxy Systems

The tensile fracture mechanics and thermo-mechanical properties of mixtures composed of two kinds of epoxy resins of different chemical structures and functional groups were studied. The base resin was a bi-functional epoxy resin based on diglycidyl ether of bisphenol-A (DGEBA) and the other resins were (a) distilled triglycidylether of meta-amino phenol (b) 1, 6–naphthalene di epoxy and (c) fluorene di epoxy. This research shows that a small number of multifunctional epoxy systems, both di- and tri-functional, can significantly increase tensile strength (14%) over neat DGEBA while having no negative impact on other mechanical properties including glass transition temperature and elastic modulus. In fact, when compared to unmodified DGEBA, the tri-functional epoxy shows a slight increase (5%) in glass transition temperature at 10 wt.% concentration. The enhanced crosslinking of DGEBA (90 wt.%)/distilled triglycidylether of meta-amino phenol (10 wt.%) blends may be the possible reason for the improved glass transition. Finally, the influence of strain rate, temperature and moisture were investigated for both the neat DGEBA and the best performing modified system. The neat DGEBA was steadily outperformed by its modified counterpart in every condition.

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