Search results for "Lewis acids"

On the enhancement of stereoselection by cooperation between chiral auxiliaries. Asymmetric diels-alder reactions with fumaric acid bis ((S)-proline …

1989

Abstract Fumaric acid bis ((S)-proline benzyl ester) amide reacts with cyclopentadiene in thermal and Lewis acid catalyzed Diels-Alder reactions to give the cycloadducts with high yields and diastereomeric ratios up to 100:1.

Heterometallic Titanium-Organic Frameworks as Dual Metal Catalysts for Synergistic Non-Buffered Hydrolysis of Nerve Agent Simulants

2020

Heterometallic metal-organic frameworks (MOFs) can offer important advantages over their homometallic counterparts to enable targeted modification of their adsorption, structural response, electronic structure, or chemical reactivity. However, controlling metal distribution in these solids still remains a challenge. The family of mesoporous titanium-organic frameworks, MUV-101(M), displays heterometallic TiM2 nodes assembled from direct reaction of Ti(IV) and M(II) salts. We use the degradation of nerve agent simulants to demonstrate that only TiFe2 nodes are capable of catalytic degradation in non-buffered conditions. By using an integrative experimental-computational approach, we rational…

Orientation of the acidity probes benzene, acetonitrile and pyridine in SAPO-5 and GaAPO-5 molecular sieves: an FTIR microscopy study

1997

The adsorption and desorption behaviour of benzene, acetonitrile (CD3CN) and pyridine for large crystals of SAPO-5 and GaAPO-5 is studied using FTIR microscopy with polarised IR radiation. From the analysis of the polarised adsorption bands it is concluded that the adsorbates are ordered in the molecular sieves at 373 K. The orientation of molecules interacting with Bronsted or Lewis acid sites and of physisorbed molecules are discussed. Benzene adsorbed at Bronsted sites is oriented with the aromatic ring parallel to the crystallographic c-axis of the molecular sieve, whereas physisorbed benzene is oriented with the aromatic ring parallel to the crystallographic a,bplane. Acetonitrile can …

Reversal of asymmetric induction in stereoselective strecker synthesis on galactosyl amine as the chiral matrix

1988

Abstract The reversal of the direction of asymmetric induction in Lewis acid catalyzed Strecker synthesis using the 2,3,4,6-tetra-O-pivaloyl-β-D-galactopyranosyl amine 1 is described. In isopropanol or tetrahydrofuran 1 had given ( R )-diastereomers of the corresponding α-amino nitriles preferably. However, in chloroform in the presence of heterogeneous zinc chloride the same auxiliary alternatively leads to an excess of the ( S )-diastereomers.

3.13 Carbohydrate Derived Auxiliaries: Amino Sugar and Glycosylamine Auxiliaries

2012

The stereodifferentiating potential of carbohydrate auxiliaries is illustrated by examples of oxazolidinones derived from amino sugars and aldimines of glycosylamines. Taking advantage of the bicyclic structure of amino sugar-derived oxazolidinones, reactions of their unsaturated or deprotonated N -acyl derivatives show an efficient exo - versus endo -differentiation. High diastereoselectivity is achieved in the syntheses of β -branched or α -substituted carboxylic acid derivatives. Imines of glycosylamines, in particular of 2,3,4,6-tetra- O -pivaloyl- β - d -galactopyranosylamine, are characterized by a conformation stabilized through the exo -anomeric effect and by their ability to coordi…

New heterogeneous catalysts for greener routes in the synthesis of fine chemicals

2007

Abstract New strong Lewis acid SnTf-MCM-41 and SnTf-UVM-7 catalysts with unimodal and bimodal pore systems were prepared in a two-step synthesis in which the triflic acid (Tf) was incorporated to previously synthesized mesoporous tin-containing silicas. The Sn incorporation inside the pore walls was carried out through the Atrane method. The SnTf-UVM-7 catalysts were prepared by aggregating nanometric mesoporous particles defining a hierarchic textural-type additional pore system. Following these procedures, catalysts with different Si/Sn ratios—21.8 to 50.8 for SnTf-MCM-41 and 18.4 for SnTf-UVM-7—were prepared. These new materials were tested in the acylation of aromatic sulfonamides using…

2018

Tetrel bonding is the noncovalent interaction of group IV elements with electron donors. It is a weak, directional interaction that resembles hydrogen and halogen bonding yet remains barely explored. Herein, we present an experimental investigation of the carbon-centered, three-center, four-electron tetrel bond, [N–C–N]+, formed by capturing a carbenium ion with a bidentate Lewis base. NMR-spectroscopic, titration-calorimetric, and reaction-kinetic evidence for the existence and structure of this species is reported. The studied interaction is by far the strongest tetrel bond reported so far and is discussed in comparison with the analogous halogen bond. The necessity of the involvement of …

Reconsidering TOF calculation in the transformation of epoxides and CO2 into cyclic carbonates

2020

Abstract The combination of Lewis acids and Lewis bases, currently defined as catalysts and co-catalysts (or promoter) respectively, in the reaction between epoxides and CO2 to give cyclic carbonates, is discussed, starting from examples in which the Lewis base was used in larger amount with respect to the Lewis acid. In these cases, turnover frequency (TOF) values have been usually calculated taking into account solely the amount of the Lewis acid employed. The occurrence of two distinct reaction pathways, one catalysed by the sole Lewis base and the other one catalysed by the Lewis acid/Lewis base couple, in which the Lewis acid alone does not play a catalytic role, should bring researche…

Lewis acid-catalyzed Beckmann rearrangement of ketoximes in ionic liquids

2009

Abstract The Beckmann rearrangement of five ketoximes was done in 17 different ionic liquids by using four Lewis acids. The effect of the type of cation and the type of anion in the ionic liquid on the rate of the rearrangement reaction and product composition is compared and discussed. The effects of the hydrophobicity and the hydrogen bonding ability of ionic liquids on the rearrangement of ketoximes were investigated, as well as the catalytical activity of the Lewis acids.

Studien zum Vorgang der Wasserstoffübertragung, 67. Endioldiester durch acylierende elektroreduktive Dimerisierung von Carbonsäurechloriden mit Lithi…

1983

Aromatische, aliphatische und aromatisch-aliphatische Carbonsaurechloride (und Anhydride) werden mit Lithiumamalgam (Li/Hg) durch acylierende reduktive Dimerisierung in wechselnden Ausbeuten (meist 70%) in cis- und/oder trans-Endioldiester 1–10 ubergefuhrt. Der Einflus des Losungsmittels auf den Reaktionsverlauf wird untersucht. Aus 2,2′-Diphensauredichlorid entsteht das Phenanthrenderivat 7, aus Phthaloyldichlorid Phthalid 8. Li/Hg wandelt Diphenyl-phosphinylchlorid in Tetraphenyldiphosphandioxid (15) um. Auf die Bestimmung der Halbstufenpotentiale von 12 Saurechloriden und vier 1,2-Diketonen grundet sich die Formulierung des Reaktionsmechanismus. 1,2-Diketone sind Zwischenprodukte der acy…