Pursuing the active species in an aluminium-based Lewis acid system for catalytic Diels–Alder cycloadditions

2017 ◽  
Vol 46 (3) ◽  
pp. 753-759 ◽  
Author(s):  
Zhizhou Liu ◽  
Rakesh Ganguly ◽  
Dragoslav Vidović

Detailed characterization of the catalytically active aluminium species supported by a bis(imino)aryl ligand has been reported.

2016 ◽  
Vol 45 (3) ◽  
pp. 1127-1137 ◽  
Author(s):  
Laura E. Riley ◽  
Antony P. Y. Chan ◽  
James Taylor ◽  
Wing Y. Man ◽  
David Ellis ◽  
...  

The compound (p-cymene)Ru[(C2B10H10)2], an effective Lewis acid catalyst, is the precursor to a number of products in which the 1,1′-bis(o-carborane) unit displays an unprecedented range of ligating modes.


2000 ◽  
Vol 78 (9) ◽  
pp. 1247-1250 ◽  
Author(s):  
Alexei A Neverov ◽  
R S Brown

Methanolysis of acetylimidazole (1) and N-acetylimidazolepentamine-Co(III) (2) was found to be markedly accelerated in the presence of La(OTf)3. Potentiometric titration of a solution of La3+(OTf-)3 gave a pKa for the metal bound CH3OH of 7.22. The kinetics of methanolysis of 1 and 2 were measured at 25°C at various pH under buffered conditions as a function of increasing La3+. Analysis of both the kinetic and potentiometric data indicates that the catalytically active species is a La3+-dimer, bridged by two methoxides, (CH3OH)nLa3+(CH3O-)2La3+(CH3OH)n. The maximum second-order rate constants for attack of the dimer on 1 and 2 are 1.50 × 103 M-1 s-1 and 1.42 × 102 M-1 s-1 respectively and both processes adhere to titration of a La3+(CH3OH) to generate the active form. The results are explained in terms of a mechanism where the methoxy-bridged La3+ dimer transiently breaks a La3+-OCH3 bond to expose both a CH3O- nucleophile and a La3+ which can act as a Lewis acid. Unlike the situation in water, the methanol results indicate that the medium greatly stabilizes and solubilizes the active dimer without the necessity of creating specially designed ligands to stabilize the dinuclear core.Key words: lanthanum ion, catalysis, methanolysis, activated amide.


1996 ◽  
Vol 61 (4) ◽  
pp. 1436-1442 ◽  
Author(s):  
D. K. Singh ◽  
James B. Springer ◽  
Patricia A. Goodson ◽  
Robert C. Corcoran

2020 ◽  
Author(s):  
Wallace Derricotte ◽  
Huiet Joseph

The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (i) a step-wise mechanism that proceeds through formation of the Z-isomer of their shared enediol intermediate, (ii) a step-wise mechanism that forms the E-isomer of the enediol, and (iii) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol<sup>-1</sup>. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.


2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.


2018 ◽  
Vol 15 (2) ◽  
pp. 221-229 ◽  
Author(s):  
Shah Bakhtiar Nasir ◽  
Noorsaadah Abd Rahman ◽  
Chin Fei Chee

Background: The Diels-Alder reaction has been widely utilised in the syntheses of biologically important natural products over the years and continues to greatly impact modern synthetic methodology. Recent discovery of chiral organocatalysts, auxiliaries and ligands in organic synthesis has paved the way for their application in Diels-Alder chemistry with the goal to improve efficiency as well as stereochemistry. Objective: The review focuses on asymmetric syntheses of flavonoid Diels-Alder natural products that utilize chiral ligand-Lewis acid complexes through various illustrative examples. Conclusion: It is clear from the review that a significant amount of research has been done investigating various types of catalysts and chiral ligand-Lewis acid complexes for the enantioselective synthesis of flavonoid Diels-Alder natural products. The results have demonstrated improved yield and enantioselectivity. Much emphasis has been placed on the synthesis but important mechanistic work aimed at understanding the enantioselectivity has also been discussed.


2016 ◽  
Author(s):  
Janelle A.F. Heitmeier ◽  
◽  
Emily S. Martin ◽  
Jordan M. Bretzfelder ◽  
D. Alex Patthoff ◽  
...  

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