A Combined Experimental and Density Functional Theory Investigation of Hydrocarbon Activation at a Cationic Platinum(II) Diimine Aqua Complex under Mild Conditions in a Hydroxylic Solvent

2000 ◽  
Vol 122 (44) ◽  
pp. 10831-10845 ◽  
Author(s):  
Hanne Heiberg ◽  
Lars Johansson ◽  
Odd Gropen ◽  
Olav B. Ryan ◽  
Ole Swang ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Aqua Complex ◽  
Functional Theory ◽  
Mild Conditions

Chlorination of Aromatics with Trichloroisocyanuric Acid (TCICA) in Brønsted-Acidic Imidazolium Ionic Liquid [BMIM(SO3H)][OTf]: an Economical, Green Protocol for the Synthesis of Chloroarenes

2007 ◽  
Vol 60 (12) ◽  
pp. 923 ◽  
Author(s):  
Abigail Hubbard ◽  
Takao Okazaki ◽  
Kenneth K. Laali
Keyword(s):  
Density Functional Theory ◽  
Ionic Liquid ◽  
Density Functional ◽  
Survey Study ◽  
Imidazolium Ionic Liquid ◽  
Functional Theory ◽  
Green Protocol ◽  
Mild Conditions ◽  
Trichloroisocyanuric Acid ◽  
Insight Into

A survey study on electrophilic chlorination of aromatics with trichloroisocyanuric acid (TCICA) in Brønsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf] is reported. The reactions are performed under very mild conditions (at ~50°C) and give good to excellent yields, depending on the substrates. Chemoselectivity for mono- v. dichlorination can be tuned by changing the arene-to-TCICA ratio and the reaction time. The survey study and competitive experiments suggest that triprotonated/protosolvated TCICA is a selective/moderately reactive transfer-chlorination electrophile. Density functional theory was used as guide to obtain further insight into the nature of the chlorination electrophile and the transfer-chlorination step.

scholarly journals Simultaneous construction of axial and planar chirality by gold/TY-Phos-catalyzed asymmetric hydroarylation

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Pei-Chao Zhang ◽  
Yin-Lin Li ◽  
Jiafeng He ◽  
Hai-Hong Wu ◽  
Zhiming Li ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Potential Application ◽  
Density Functional ◽  
Catalyst System ◽  
High Yield ◽  
Gold Complex ◽  
Functional Theory ◽  
Planar Chirality ◽  
Mild Conditions ◽  
Cationic Gold

AbstractThe simultaneous construction of two different chiralities via a simple operation poses considerable challenge. Herein a cationic gold-catalyzed asymmetric hydroarylation of ortho-alkynylaryl ferrocenes derivatives is developed, which enable the simultaneous construction of axial and planar chirality. The here identified TY-Phos derived gold complex is responsible for the high yield, good diastereoselectivity (>20:1 dr), high enantioselectivities (up to 99% ee) and mild conditions. The catalyst system also shows potential application in the synthesis of chiral biaryl compounds. The cause of high enantioselectivity of this hydroarylation is investigated with density functional theory caculation.

scholarly journals Highly Diastereo- and Enantioselective Synthesis of Quinuclidine Derivatives by an Iridium-Catalyzed Intramolecular Allylic Dearomatization Reaction

CCS Chemistry ◽  
2019 ◽  
pp. 106-116 ◽  
Author(s):  
Lin Huang ◽  
Yue Cai ◽  
Hui-Jun Zhang ◽  
Chao Zheng ◽  
Li-Xin Dai ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Catalytic System ◽  
Density Functional ◽  
Functional Group ◽  
Enantioselective Synthesis ◽  
Large Array ◽  
Functional Theory ◽  
Mild Conditions ◽  
Group Diversity

Asymmetric construction of quinuclidine derivatives has been realized by an iridium-catalyzed allylic dearomatization reaction. The catalytic system, derived from [Ir(cod)Cl] 2 and the Feringa ligand, tolerates a broad range of substrates. A large array of quinuclidine derivatives can be obtained under mild conditions in good to excellent yields (68%–96%), diastereoselectivity (up to >20/1 dr), and enantioselectivity (up to >99% ee). These products feature versatile functional group diversity and can undergo diverse transformations. A model that accounts for the origin of the stereoselectivity has been proposed based on density functional theory (DFT) calculations.

Electrochemical Reduction of Homo– and Hetero–tri(aryl)borohydrides

2019 ◽  
Author(s):  
Robin Blagg ◽  
Elliot Lawrence ◽  
Gregory Wildgoose
Keyword(s):  
Density Functional Theory ◽  
Cyclic Voltammetry ◽  
Density Functional ◽  
Lewis Base ◽  
Dft Studies ◽  
Computational Investigation ◽  
Functional Theory ◽  
Mild Conditions ◽  
Hydride Ion ◽  
Cyclic Voltammetry Data

<p> Authentic terminal homo– and hetero–tri(aryl)borohydrides of the form [HB(C<sub>6</sub>F<sub>5</sub>)<sub><i>x</i></sub>{<i>m</i>,<i>m</i>–(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sub><i>y</i></sub>(C<sub>6</sub>Cl<sub>5</sub>)<sub><i>z</i></sub>]<sup>−</sup><sup></sup> have been synthesised by reaction of their parent borane with a hydride source; their electrochemical properties have been studied, together with a computational investigation using density functional theory (DFT). The three of these compounds incorporating at least two pentachlorophenyl rings have been identified as, upon electrochemical oxidation, regenerating their parent borane, one of the essential steps (together with rapid cleavage under mild conditions of H<sub>2</sub> together with an appropriate Lewis base), in implementing the electrochemically coupled – frustrated Lewis pair concept. The resulting mechanism upon oxidation is supported by modelling the cyclic voltammetry data obtained. The DFT studies have allowed for the structures of these compounds to be assessed, along with quantifying their hydride ion affinities (HIAs).</p>

A DFT-Weaving of Single Component Bifunctional Organocatalysts for Carbon dioxide/Propylene Oxide Coupling Reaction

2021 ◽  
Author(s):  
Morad El-Hendawy ◽  
Ibtesam Desoky ◽  
Mahmoud M. Mohamed
Keyword(s):  
Carbon Dioxide ◽  
Density Functional Theory ◽  
Dft Calculations ◽  
Propylene Oxide ◽  
Density Functional ◽  
Coupling Reaction ◽  
Single Component ◽  
Coupling Reactions ◽  
Functional Theory ◽  
Mild Conditions

The work aims to develop single-component bifunctional organic catalysts capable of effectively coupling reactions between CO2 and propylene epoxide (PO) under mild conditions using density functional theory (DFT) calculations. The...

Electrochemical Reduction of Homo– and Hetero–tri(aryl)borohydrides

2019 ◽  
Author(s):  
Robin Blagg ◽  
Elliot Lawrence ◽  
Gregory Wildgoose
Keyword(s):  
Density Functional Theory ◽  
Cyclic Voltammetry ◽  
Density Functional ◽  
Lewis Base ◽  
Dft Studies ◽  
Computational Investigation ◽  
Functional Theory ◽  
Mild Conditions ◽  
Hydride Ion ◽  
Cyclic Voltammetry Data

<p> Authentic terminal homo– and hetero–tri(aryl)borohydrides of the form [HB(C<sub>6</sub>F<sub>5</sub>)<sub><i>x</i></sub>{<i>m</i>,<i>m</i>–(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sub><i>y</i></sub>(C<sub>6</sub>Cl<sub>5</sub>)<sub><i>z</i></sub>]<sup>−</sup><sup></sup> have been synthesised by reaction of their parent borane with a hydride source; their electrochemical properties have been studied, together with a computational investigation using density functional theory (DFT). The three of these compounds incorporating at least two pentachlorophenyl rings have been identified as, upon electrochemical oxidation, regenerating their parent borane, one of the essential steps (together with rapid cleavage under mild conditions of H<sub>2</sub> together with an appropriate Lewis base), in implementing the electrochemically coupled – frustrated Lewis pair concept. The resulting mechanism upon oxidation is supported by modelling the cyclic voltammetry data obtained. The DFT studies have allowed for the structures of these compounds to be assessed, along with quantifying their hydride ion affinities (HIAs).</p>

scholarly journals Selective valorization of lignin to phenol by direct transformation of Csp2–Csp3 and C–O bonds

2020 ◽  
Vol 6 (45) ◽  
pp. eabd1951
Author(s):  
Jiang Yan ◽  
Qinglei Meng ◽  
Xiaojun Shen ◽  
Bingfeng Chen ◽  
Yang Sun ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Aromatic Ring ◽  
Density Functional ◽  
Zeolite Catalyst ◽  
Reaction Pathway ◽  
Scale Up ◽  
Functional Theory ◽  
Direct Transformation ◽  
Mild Conditions ◽  
Bond Breakage

Phenol is an important commodity chemical in the industry, which is currently produced using fossil feedstocks. Here, we report a strategy to produce phenol from lignin by directly deconstructing Csp2–Csp3 and C–O bonds under mild conditions. It was found that zeolite catalyst could efficiently catalyze both the direct Csp2–Csp3 bond breakage to remove propyl structure and aliphatic β carbon–oxygen (Cβ–O) bond hydrolysis to form OH group on the aromatic ring. The yield of phenol could reach 10.9 weight % with a selectivity of 91.8%. In this unique route, water was the only reactant besides lignin. A scale-up experiment showed that 4.1 g of pure phenol could be obtained from 50.0 g of lignin. The reaction pathway was proposed by a combination of control experiments and density functional theory studies. This work opens the way for producing phenol from lignin by direct transformation of Csp2–Csp3 and C–O bonds in lignin.

Doping effects on the geometric and electronic structure of tin clusters

2019 ◽  
Vol 21 (44) ◽  
pp. 24478-24488 ◽  
Author(s):  
Martin Gleditzsch ◽  
Marc Jäger ◽  
Lukáš F. Pašteka ◽  
Armin Shayeghi ◽  
Rolf Schäfer
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Density Functional ◽  
Beam Deflection ◽  
Functional Theory ◽  
Doping Effects ◽  
Depth Analysis ◽  
Trajectory Simulations

In depth analysis of doping effects on the geometric and electronic structure of tin clusters via electric beam deflection, numerical trajectory simulations and density functional theory.

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