Theoretical Confirmation of the Reaction Mechanism Leading to Regioselective Formation of Thiazolidin-4-one from Bromoacetic Acid Derivatives

2007 ◽  
Vol 72 (10) ◽  
pp. 1435-1445 ◽  
Author(s):  
Ladislav Janovec ◽  
Stanislav Böhm ◽  
Ivan Danihel ◽  
Ján Imrich ◽  
Pavol Kristian ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Regioselective Synthesis ◽  
Bromoacetic Acid ◽  
Phenyl Derivative

A regioselective synthesis of 3-alkyl-2-[(anthracen-9-yl)imino]thiazolidin-4-ones 2a-2e and 2-(alkylimino)-3-(anthracen-9-yl)thiazolidin-4-ones 3a-3e from appropriate thioureas using methyl bromoacetate or bromoacetyl bromide, respectively, has been rationalized by DFT calculations of model thiourea and its phenyl derivative. The proposed mechanism indicates that the regioselective formation of the target thiazolidinones is a consequence of a different reactivity of the reagents and a varying stability of the intermediates, 1-alkyl-3-(anthracen-9-yl)-2-[(methoxycarbonyl)methyl]isothioureas 4a-4e and 1-alkyl-3-(anthracen-9-yl)-2-(bromoacetyl)isothioureas 6a-6e.

Reactions of an Aluminium(I) Reagent with 1,2-, 1,3- and 1,5-Dienes: Dearomatisation, Reversibility, and a Pericyclic Mechanism

2019 ◽  
Author(s):  
Clare Bakewell ◽  
Martí Garçon ◽  
Richard Y Kong ◽  
Louisa O'Hare ◽  
Andrew J. P. White ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Transition State ◽  
Reaction Pathways ◽  
Aromatic Rings ◽  
Aromatic Character ◽  
Pericyclic Reaction

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.

scholarly journals Catalytic mechanism of the colistin resistance protein MCR-1

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.

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

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 <i>η</i>3-coordination of the 2-phosphaethynthiolate anion in the complex (PN)<sub>2</sub>La(SCP) (<b>2</b>) [PN = N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate bridged (PN)<sub>2</sub>La(<i>μ</i>-1,3-SCN)<sub>2</sub>La(PN)<sub>2</sub> (<b>3</b>) and azide bridged (PN)<sub>2</sub>La(<i>μ</i>-1,3-N3)<sub>2</sub>La(PN)<sub>2</sub> (<b>4</b>) complexes indicates that the [SCP]<sup>–</sup> 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]<sup>–</sup> ligand to the LUMO of complex <b>2</b>, rendering it the ideal precursor for the first functionalization of the [SCP]<sup>–</sup> anion. Complex <b>2</b> was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]<sup>–</sup> ligand to form the first CAAC stabilized group 15 – group 16 fulminate-type complexes (PN)<sub>2</sub>La{SPC(<sup>R</sup>CAAC)} (<b>5a,b</b>) (R = Ad, Me). A detailed reaction mechanism for the SCP to SPC isomerization is proposed based on DFT calculations.

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

2015 ◽  
Vol 17 (17) ◽  
pp. 11499-11508 ◽  
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.

scholarly journals On the catalytic transfer hydrogenation of nitroarenes by a cubane-type Mo3S4 cluster hydride: disentangling the nature of the reaction mechanism

2019 ◽  
Vol 21 (31) ◽  
pp. 17221-17231 ◽  
Author(s):  
Vicent S. Safont ◽  
Iván Sorribes ◽  
Juan Andrés ◽  
Rosa Llusar ◽  
Mónica Oliva ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Transfer Hydrogenation ◽  
Catalytic Transfer Hydrogenation ◽  
Efficient Catalyst ◽  
Highly Efficient ◽  
Catalytic Transfer

Transfer hydrogenation cluster catalysis operates through a panoply of cycles, according to DFT calculations, affording a highly efficient catalyst.

Catalytic polymerization of naphthalene by HF/BF3 super acid: an ab initio density functional theory study

2018 ◽  
Vol 20 (36) ◽  
pp. 23311-23319 ◽  
Author(s):  
Po-Yu Yang ◽  
Hsing-Yin Chen ◽  
Shin-Pon Ju ◽  
Chia-Lin Chang ◽  
Gao-Shee Leu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Ab Initio ◽  
Density Functional ◽  
Catalytic Polymerization ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Detailed Reaction Mechanism ◽  
Super Acid

The detailed reaction mechanism of naphthalene catalytic polymerization by HF/BF3 has been investigated by DFT calculations and the directionality of the naphthalene-derived mesophase molecule has been explained.

Oxygen reduction reaction mechanism on P, N co-doped graphene: a density functional theory study

2019 ◽  
Vol 43 (48) ◽  
pp. 19308-19317 ◽  
Author(s):  
Zhao Liang ◽  
Chao Liu ◽  
Mingwei Chen ◽  
Xiaopeng Qi ◽  
Pramod Kumar U. ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Dft Calculations ◽  
Density Functional ◽  
Reduction Reaction ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Doped Graphene ◽  
Co Doped

DFT calculations confirmed that the P–N coupled site changed the ORR pathway and improved the catalytic activity compared with single doping.

Well-defined nickel(II) tetrazole-saccharinate complex as homogeneous catalyst on the reduction of aldehydes: scope and reaction mechanism

2020 ◽  
Vol 92 (1) ◽  
pp. 151-166 ◽  
Author(s):  
Luís M. T. Frija ◽  
Bruno G. M. Rocha ◽  
Maxim L. Kuznetsov ◽  
Lília I. L. Cabral ◽  
M. Lurdes S. Cristiano ◽  
...  
Keyword(s):  
Experimental Data ◽  
Reaction Mechanism ◽  
Transition Metal ◽  
Dft Calculations ◽  
Microwave Power ◽  
Low Temperatures ◽  
Nickel Complex ◽  
Transition Metal Catalysts ◽  
Homogeneous Catalyst ◽  
First Time

AbstractA new (tetrazole-saccharin)nickel complex is shown to be a valuable catalyst for the hydrosilative reduction of aldehydes under microwave radiation at low temperatures. With typical 1 mol% content of the catalyst (microwave power range of 5–15 W) most reactions are complete within 30 min. The Ni(II)-catalyzed reduction of aldehydes, with a useful scope, was established for the first time by using this catalyst, and is competitive with the most effective transition-metal catalysts known for such transformation. The catalyst reveals tolerance to different functional groups, is air and moisture stable, and is readily prepared in straightforward synthetic steps. Supported by experimental data and DFT calculations, a plausible reaction mechanism involving the new catalytic system is outlined.

Regioselective Synthesis of 2(1H)-Pyridinones from β-Aminoenones and Malononitrile. Reaction Mechanism

1999 ◽  
Vol 64 (26) ◽  
pp. 9493-9498 ◽  
Author(s):  
Angel Alberola ◽  
Luis A. Calvo ◽  
Alfonso González Ortega ◽  
M. Carmen Sañudo Ruíz ◽  
Pedro Yustos ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Regioselective Synthesis
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