Theoretical Calculation on Regioselectivity and Solvation Effect in B-H Activation of O-carborane Guided by Directing Group

The reactions of an aluminium(I) reagent with a series of 1,2-, 1,3- and 1,5-dienes are reported. In the case of 1,3-dienes the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene containing products. This mechanism has been interrogated by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4+1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4+1) cycloaddition includes dienes that are either in part, or entirely, contained within aromatic rings. In these cases, reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2- or 1,5-dienes complementary reactivity is observed; the orthogonal nature of the C=C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavour a (4+1) cycloaddition. Rather, reaction pathways are determined by an initial (2+1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C=C π-bond leading to complex organometallic products that incorporate fused hydrocarbon rings.

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Reaction mechanism of synthetic thorium sulfides: theoretical calculation study

Journal of Molecular Modeling ◽

10.1007/s00894-020-04392-7 ◽

2020 ◽

Vol 26 (6) ◽

Author(s):

Huifeng Zhao ◽

Peng Li ◽

Meigang Duan ◽

Feng Xie ◽

Jie Ma

Keyword(s):

Reaction Mechanism ◽

Theoretical Calculation

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Catalytic mechanism of the colistin resistance protein MCR-1

Organic & Biomolecular Chemistry ◽

10.1039/d0ob02566f ◽

2021 ◽

Author(s):

Reynier Suardíaz ◽

Emily Lythell ◽

Philip Hinchliffe ◽

Marc van der Kamp ◽

James Spencer ◽

...

Keyword(s):

Reaction Mechanism ◽

Antimicrobial Resistance ◽

Dft Calculations ◽

Catalytic Reaction ◽

Catalytic Mechanism ◽

Cluster Models ◽

Colistin Resistance ◽

Resistance Protein ◽

Catalytic Reaction Mechanism

Elucidation of the catalytic reaction mechanism of MCR-1 enzyme, responsible for the antimicrobial resistance to colistin, using DFT calculations on cluster models.

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Study the solvation effect on 6-phenyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile derivatives by TD- DFT calculations and molecular dynamics simulations

Journal of Molecular Structure ◽

10.1016/j.molstruc.2019.127056 ◽

2020 ◽

Vol 1200 ◽

pp. 127056 ◽

Cited By ~ 5

Author(s):

Mahmoud K. Abdel-Latif ◽

H.R. Abd El-Mageed ◽

Hussein S. Mohamed ◽

F.M. Mustafa

Keyword(s):

Molecular Dynamics ◽

Dft Calculations ◽

Molecular Dynamics Simulations ◽

Solvation Effect ◽

Td Dft ◽

Dynamics Simulations

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Palladium-Catalysed C–F Alumination of Fluorobenzenes: Mechanistic Diversity and Origin of Selectivity

10.26434/chemrxiv.12053601.v1 ◽

2020 ◽

Author(s):

Feriel Rekhroukh ◽

Wenyi Chen ◽

Ryan Brown ◽

Andrew J. P. White ◽

Mark Crimmin

Keyword(s):

Dft Calculations ◽

Bond Activation ◽

Oxidative Addition ◽

Fluorine Content ◽

Model Potential ◽

Heterometallic Complex ◽

Experimental Support ◽

Highly Active ◽

Reaction Proceeds ◽

Directing Group

A palladium pre-catalyst, [Pd(PCy3)2] is reported for the efficient and selective C–F alumination of fluorobenzenes with the aluminium(I) reagent [{(ArNCMe)2CH}Al] (1, Ar = 2,6-di-iso-propylphenyl). The catalytic protocol results in the transformation of sp2 C–F bonds to sp2 C–Al bonds and provides a route into reactive organoaluminium complexes (2a-h) from fluorocarbons. The catalyst is highly active. Reactions proceed within 5 minutes at 25 ºC (and at appreciable rates at even –50 ºC) and the scope includes low-fluorine-content substrates such as fluorobenzene, difluorobenzenes and trifluorobenzenes. The reaction proceeds with complete chemoselectivity (C–F vs C–H) and high regioselectivities ( >90% for C–F bonds adjacent to the most acidic C–H sites). The heterometallic complex [Pd(PCy3)(1)2] was shown to be catalytically competent. Catalytic C–F alumination proceeds with a KIE of 1.1–1.3. DFT calculations have been used to model potential mechanisms for C–F bond activation. These calculations suggest that two competing mechanisms may be in operation. Pathway 1 involves a ligand-assisted oxidative addition to [Pd(1)2] and leads directly to the product. Pathway 2 involves a stepwise C–H to C–F functionalisation mechanism in which the C–H bond is broken and reformed along the reaction coordinate, allowing it to act as a directing group for the adjacent C–F site. This second mechanism explains the experimentally observed regioselectivity. Experimental support for this C–H activation playing a key role in C–F alumination was obtained by employing [{(MesNCMe)2CH}AlH2] (3, Mes = 2,4,6-trimethylphenyl) as a reagent in place of 1. In this instance, the kinetic C–H alumination intermediate could be isolated. Under catalytic conditions this intermediate converts to the thermodynamic C–F alumination product.

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Unprecedented η3-Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)

10.26434/chemrxiv.13567400 ◽

2021 ◽

Author(s):

Fabian A. Watt ◽

Lukas Burkhardt ◽

Roland Schoch ◽

Stefan Mitzinger ◽

Matthias Bauer ◽

...

Keyword(s):

Reaction Mechanism ◽

Dft Calculations ◽

Coordination Mode ◽

Quantum Mechanical ◽

Structural Comparison ◽

Anion Complex ◽

Steric Factors ◽

Group 15 ◽

Detailed Reaction Mechanism ◽

The Ideal

We present the unprecedented η3-coordination of the 2-phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN = N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate bridged (PN)2La(μ-1,3-SCN)2La(PN)2 (3) and azide bridged (PN)2La(μ-1,3-N3)2La(PN)2 (4) complexes indicates that the [SCP]– coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π-orbital of the [SCP]– ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP]– anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]– ligand to form the first CAAC stabilized group 15 – group 16 fulminate-type complexes (PN)2La{SPC(RCAAC)} (5a,b) (R = Ad, Me). A detailed reaction mechanism for the SCP to SPC isomerization is proposed based on DFT calculations.

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The reactivity of stoichiometric tungsten oxide clusters towards carbon monoxide: the effects of cluster sizes and charge states

Physical Chemistry Chemical Physics ◽

10.1039/c5cp00529a ◽

2015 ◽

Vol 17 (17) ◽

pp. 11499-11508 ◽

Cited By ~ 4

Author(s):

Shu-Juan Lin ◽

Jing Cheng ◽

Chang-Fu Zhang ◽

Bin Wang ◽

Yong-Fan Zhang ◽

...

Keyword(s):

Carbon Monoxide ◽

Reaction Mechanism ◽

Dft Calculations ◽

Tungsten Oxide ◽

Charge States

DFT calculations were carried out to study the reaction mechanism for tungsten oxide clusters with CO.

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Palladium-catalyzed directing group assisted and regioselectivity reversed cyclocarbonylation of arylallenes with 2-iodoanilines

Organic Chemistry Frontiers ◽

10.1039/d0qo01404d ◽

2021 ◽

Author(s):

Jian-Shu Wang ◽

Lingyun Yao ◽

Jun Ying ◽

Xiaoling Luo ◽

Xiao-Feng Wu

Keyword(s):

Dft Calculations ◽

Palladium Catalyzed ◽

Directing Group

A palladium-catalyzed regioselective cyclocarbonylation of N-(2-pyridyl)sulfonyl (N-SO2Py)-2-iodoanilines with allenes was developed. The regioselectivity of arylallenes was reversed. Control experiments and DFT calculations were performed to understand the reaction details.

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