scholarly journals Ligand Constraint Induced Peroxide Activation for Electrophilic Reactivity

2021 ◽  
Author(s):  
Kallol Ray ◽  
Anirban Chandra ◽  
Mursaleem Ansari ◽  
Inés Monte-Pérez ◽  
Subrata Kundu ◽  
...  
Keyword(s):  
Electrophilic Reactivity ◽  
Peroxide Activation

scholarly journals Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF

2017 ◽  
Vol 139 (20) ◽  
pp. 7062-7070 ◽  
Author(s):  
Kiyoung Park ◽  
Ning Li ◽  
Yeonju Kwak ◽  
Martin Srnec ◽  
Caleb B. Bell ◽  
...  
Keyword(s):  
Heme Iron ◽  
Non Heme Iron ◽  
Electrophilic Reactivity ◽  
Peroxide Activation

scholarly journals Ligand Constraint Induced Peroxide Activation for Electrophilic Reactivity

2021 ◽  
Author(s):  
Kallol Ray ◽  
Anirban Chandra ◽  
Mursaleem Ansari ◽  
Inés Monte-Pérez ◽  
Subrata Kundu ◽  
...  
Keyword(s):  
Electrophilic Reactivity ◽  
Peroxide Activation

Spectroscopic investigations and DFT studies of synthesized 4-acetamidophenyl 3,4,5-trimethoxybenzoate and 4-acetyl phenyl 3,4,5-trimethoxybenzoate a novel conjugate of gallic acid

2020 ◽  
Vol 17 ◽  
Author(s):  
Sangeeta Srivastava ◽  
Nadeem Ahmad Ansari ◽  
Sadaf Aleem
Keyword(s):  
Gallic Acid ◽  
Density Functional ◽  
Energy Gap ◽  
Basis Set ◽  
Major Constituent ◽  
Orbital Energy ◽  
Reactivity Descriptors ◽  
Homo And Lumo ◽  
Electrophilic Reactivity ◽  
Global And Local

: Gallic acid is abundantly found in amla (Phyllanthus emblica), a deciduous of the family phyllanthaceae. Gallic acid, the major constituent of the plant was methylated to 3,4,5 trimethoxy gallic acid, which then underwent steglich esterification first with paracetamol and then with 4-hydroxy acetophenone to yield 4-acetamidophenyl 3,4,5-trimethoxybenzoate and 4-acetyl phenyl 3,4,5-trimethoxybenzoate “respectively”. 1H NMR, 13C NMR, UV, FT-IR and mass spectroscopy were used to characterize the synthesized compounds. Density functional theory (B3YLP) using 6-31G (d,p) basis set have been used for quantum chemical calculations. AIM (Atom in molecule) approach depicted weak molecular interactions within the molecules whereas the reactive site and reactivity within the molecule were examined by global and local reactivity descriptors. The HOMO and LUMO energies and frontier orbital energy gap were calculated by time dependant DFT approach using IEFPCM model. Small value for HOMO–LUMO energy gap indicated that easier charge transfer occurs within compound 4. The nucleophilic and electrophilic reactivity were determined by MEP (molecular electrostatic potential) experiment. Polarizability, dipole moment, and first hyperpolarizability values were calculated to depict the NLO (nonlinear optical) property of both the synthesized compounds. The antimicrobial activity was also carried out and broad spectrum antibacterial activity against several strains of bacteria and certain unicellular fungi were exhibited by synthesized compound 3.

scholarly journals RuIII(edta) mediated oxidation of azide in the presence of hydrogen peroxide. Azide versus peroxide activation

2014 ◽  
Vol 43 (8) ◽  
pp. 3087-3094 ◽  
Author(s):  
Debabrata Chatterjee ◽  
Alicja Franke ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Peroxide Activation ◽  
Mediated Oxidation

Investigation of the electrophilic reactivity of the cytotoxic marine alkaloid discorhabdin B

2012 ◽  
Vol 10 (15) ◽  
pp. 3092 ◽  
Author(s):  
Cary F. C. Lam ◽  
Tanja Grkovic ◽  
A. Norrie Pearce ◽  
Brent R. Copp
Keyword(s):  
Marine Alkaloid ◽  
Electrophilic Reactivity

Technical–Economic Analysis of Hydrogen Peroxide Activation by a Sacrificial Anode: Comparison of Two Exchange Membranes

2021 ◽  
Author(s):  
Jhonatan J. Hermosillo-Nevárez ◽  
Yaneth A. Bustos-Terrones ◽  
Jesús G. Rangel-Peraza ◽  
María M. Armendáriz-Ontiveros ◽  
Leonel E. Amábilis-Sosa ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Economic Analysis ◽  
Sacrificial Anode ◽  
Peroxide Activation

Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

2002 ◽  
Vol 1 (10) ◽  
pp. 763-773 ◽  
Author(s):  
Jóhannes Reynisson ◽  
Robert Wilbrandt ◽  
Vibeke Brinck ◽  
Bo W. Laursen ◽  
Kasper Nørgaard ◽  
...  
Keyword(s):  
Ground State ◽  
Singlet State ◽  
Excited Singlet State ◽  
Excited Singlet ◽  
Electrophilic Reactivity

Mechanisms of aromatic nucleophilic substitution by the ambident thiocyanate ion

1973 ◽  
Vol 26 (2) ◽  
pp. 273 ◽  
Author(s):  
DE Giles ◽  
AJ Parker
Keyword(s):  
Nucleophilic Substitution ◽  
Transition States ◽  
Reactivity Ratio ◽  
Substitution Reactions ◽  
Aromatic Nucleophilic Substitution ◽  
Thiocyanate Ion ◽  
Sn2 Reactions ◽  
Leaving Group ◽  
Electrophilic Reactivity ◽  
Saturated Carbon Atom

Sulphur/nitrogen reactivity ratios in a series of aromatic nucleophilic substitution reactions of ambident thiocyanate ion have been determined. There are profound differences from the pattern found in SN2 reactions at a saturated carbon atom. Abnormal transition states, involving interactions between entering and leaving group, are likely in the bond-breaking step of the intermediate complex in reactions of thiocyanate ion with 1-fluoro-2,4-dinitrobenzene and with 2,4- dinitrophenyl 4-toluenesulphonate. The nitro-substituted aryl thiocyanates are shown to be tri-functional electrophiles, with reactive centres at aromatic carbon, at cyanide carbon, and at sulphur. Aryl 4-toluenesulphonates are bifunctional electrophiles with reactive centres at aryl carbon and sulphonyl sulphur. The site of attack by nucleophiles depends on the nature of the nucleophile. The sulphur/nitrogen reactivity ratio of ambident SCN-, and the electrophilic reactivity of tri- and bi-functional substrates, are in most instances consistent with the Hard and Soft Acids and Bases principle. Exceptions to the principle in some instances reveal differences between the SNAr and SN2 mechanisms, and in others indicate abnormal transition states.

scholarly journals Expanding Roles for Organoboron Compounds – Versatile and Valuable Molecules for Synthetic, Biological and Medicinal Chemistry

2007 ◽  
Vol 60 (11) ◽  
pp. 795 ◽  
Author(s):  
Nicos A. Petasis
Keyword(s):  
Medicinal Chemistry ◽  
Structural Characteristics ◽  
Boronic Acids ◽  
Bioactive Molecules ◽  
Organoboron Compounds ◽  
Physiological Conditions ◽  
Present Essay ◽  
Electrophilic Reactivity ◽  
Metal Catalyzed ◽  
New Applications

The present essay offers an overview of the latest developments in the chemistry of organoboron compounds. The unique structural characteristics and the versatile reactivity profile of organoboron compounds continue to expand their roles in several areas of chemistry. A growing number of boron-mediated reactions have become vital tools for synthetic chemistry, particularly in asymmetric synthesis, metal-catalyzed processes, acid catalysis, and multicomponent reactions. As a result, boronic acids and related molecules have now evolved as major players in synthetic and medicinal chemistry. Moreover, their remnant electrophilic reactivity, even under physiological conditions, has allowed their incorporation in a growing number of bioactive molecules, including bortezomib, a clinically approved anticancer agent. Finally, the sensitive and selective binding of boronic acids to diols and carbohydrates has led to the development of a growing number of novel chemosensors for the detection, quantification, and imaging of glucose and other carbohydrates. There is no doubt that the chemistry of organoboron compounds will continue to expand into new discoveries and new applications in several fields of science.

scholarly journals Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C–H Amination vs. C=C Aziridination

Catalysts ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 292
Author(s):  
Juping Wang ◽  
Kangcheng Zheng ◽  
Ting Li ◽  
Xiaojing Zhan
Keyword(s):  
Density Functional ◽  
Structural Features ◽  
High Reactivity ◽  
Strong Electron ◽  
Functional Theory ◽  
Design Elements ◽  
Nitrene Transfer ◽  
Electrophilic Reactivity ◽  
High Valent ◽  
Orbital Character

The reactivity, mechanism and chemoselectivity of the Mn-catalyzed intramolecular C–H amination versus C=C aziridination of allylic substrate cis-4-hexenylsulfamate are investigated by BP86 density functional theory computations. Emphasis is placed on the origins of high reactivity and high chemoselectivity of Mn catalysis. The N p orbital character of frontier orbitals, a strong electron-withdrawing porphyrazine ligand and a poor π backbonding of high-valent MnIII metal to N atom lead to high electrophilic reactivity of Mn-nitrene. The calculated energy barrier of C–H amination is 9.9 kcal/mol lower than that of C=C aziridination, which indicates that Mn-based catalysis has an excellent level of chemoselectivity towards C–H amination, well consistent with the experimental the product ratio of amintion-to-aziridination I:A (i.e., (Insertion):(Aziridination)) >20:1. This extraordinary chemoselectivity towards C–H amination originates from the structural features of porphyrazine: a rigid ligand with the big π-conjugated bond. Electron-donating substituents can further increase Mn-catalyzed C–H amination reactivity. The controlling factors found in this work may be considered as design elements for an economical and environmentally friendly C–H amination system with high reactivity and high chemoselectivity.

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