scholarly journals Sulfation of Diethylaminoethyl-Cellulose: QTAIM Topological Analysis and Experimental and DFT Studies of the Properties

ACS Omega ◽  
2021 ◽  
Author(s):  
Aleksandr Kazachenko ◽  
Feride Akman ◽  
Mouna Medimagh ◽  
Noureddine Issaoui ◽  
Natalya Vasilieva ◽  
...  
Keyword(s):  
Topological Analysis ◽  
Dft Studies ◽  
Diethylaminoethyl Cellulose

The Foundations of Topological Analysis: A Straightforward Introduction

1981 ◽  
Author(s):  
K. G. Binmore
Keyword(s):  
Topological Analysis

Stereodivergent Alkyne Hydrofluorination Using a Simple Practical Reagent

2020 ◽  
Author(s):  
Rui Guo ◽  
Xiaotian Qi ◽  
Hengye Xiang ◽  
Paul Geaneoates ◽  
Ruihan Wang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Biologically Active ◽  
Dft Studies ◽  
Thermodynamic Control ◽  
Important Goal ◽  
Peptide Bonds ◽  
Metal Free ◽  
Vinyl Cation ◽  
E And Z Isomers ◽  
Vinyl Fluorides

Vinyl fluorides play an important role in drug development as they serve as bioisosteres for peptide bonds and are found in a range of biologically active molecules. The discovery of safe, general and practical procedures to prepare vinyl fluorides remains an important goal and challenge for synthetic chemistry. Here we introduce an inexpensive and easily-handled reagent and report simple, scalable, and metal-free protocols for the regioselective and stereodivergent hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These conditions were suitable for a diverse collection of alkynes, including several highly-functionalized pharmaceutical derivatives. Mechanistic and DFT studies support C–F bond formation through a vinyl cation intermediate, with the (E)- and (Z)-hydrofluorination products forming under kinetic and thermodynamic control, respectively.<br>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Radical Capture at Ni(II) Complexes: C-C, C-N, and C-O Bond Formation

2019 ◽  
Author(s):  
Abolghasem (Gus) Bakhoda ◽  
Stefan Wiese ◽  
Christine Greene ◽  
Bryan C. Figula ◽  
Jeffery A. Bertke ◽  
...  
Keyword(s):  
Functional Groups ◽  
Bond Formation ◽  
Dft Studies ◽  
Bond Forming ◽  
Aryl Amines ◽  
Shed Light ◽  
Competing Pathways

<p>The dinuclear b-diketiminato Ni<sup>II</sup><i>tert</i>-butoxide {[Me<sub>3</sub>NN]Ni}<sub>2</sub>(<i>μ</i>-O<i><sup>t</sup></i>Bu)<sub>2 </sub>(<b>2</b>), synthesized from [Me<sub>3</sub>NN]Ni(2,4-lutidine) (<b>1</b>) and di-<i>tert</i>-butylperoxide, is a versatile precursor for the synthesis of a series of Ni<sup>II</sup>complexes [Me<sub>3</sub>NN]Ni-FG to illustrate C-C, C-N, and C-O bond formation at Ni<sup>II </sup>via radicals. {[Me<sub>3</sub>NN]Ni}<sub>2</sub>(<i>μ</i>-O<i><sup>t</sup></i>Bu)<sub>2 </sub>reacts with nitromethane, alkyl and aryl amines, acetophenone, benzamide, ammonia and phenols to deliver corresponding mono- or dinuclear [Me<sub>3</sub>NN]Ni-FG species (FG = O<sub>2</sub>NCH<sub>2</sub>, R-NH, ArNH, PhC(O)NH, PhC(O)CH<sub>2</sub>, NH<sub>2</sub>and OAr). Many of these Ni<sup>II </sup>complexes are capable of capturing the benzylic radical PhCH(•)CH<sub>3 </sub>to deliver corresponding PhCH(FG)CH<sub>3 </sub>products featuring C-C, C-N or C-O bonds. DFT studies shed light on the mechanism of these transformations and suggest two competing pathways that depend on the nature of the functional groups. These radical capture reactions at [Ni<sup>II</sup>]-FG complexes outline key C-C, C-N, and C-O bond forming steps and suggest new families of nickel radical relay catalysts.</p>

DIMENSIONING OF THE FRONTAL SUSPENSION SYSTEM OF THE DOUBLE-A TYPE THROUGH TOPOLOGICAL ANALYSIS.

2017 ◽  
Author(s):  
Tiago Ferreira ◽  
Thiago Moreira ◽  
Gustavo Melchiades ◽  
Lucas Ferreira ◽  
Diógenes Sena de França e Silva
Keyword(s):  
Topological Analysis ◽  
Suspension System

DFT studies of copper complexes with biphenyldiimino dithioether II. Mechanical strain

Polyhedron ◽  
2006 ◽  
Vol 25 (13) ◽  
pp. 2559-2564 ◽  
Author(s):  
Martin Breza ◽  
Jozef Kožíšek
Keyword(s):  
Copper Complexes ◽  
Mechanical Strain ◽  
Dft Studies
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