Oxidomolybdenum complexes for acid catalysis using alcohols as solvents and reactants

2016 ◽  
Vol 6 (13) ◽  
pp. 5207-5218 ◽  
Author(s):  
Ana C. Gomes ◽  
Patrícia Neves ◽  
Luís Cunha-Silva ◽  
Anabela A. Valente ◽  
Isabel S. Gonçalves ◽  
...  
Keyword(s):  
Acid Catalysis ◽  
Acid Catalysed Reactions

With ethanol as solvent and reactant, a molybdenum (pre)catalyst promotes selective acid-catalysed reactions. Depending on the conditions, the MoVIcomplex is converted to MoVIoxidoalkoxido, MoVoxido-bridged dinuclear, and MoVIoctanuclear complexes.

Catalysis by montmorillonites

Clay Minerals ◽  
1983 ◽  
Vol 18 (4) ◽  
pp. 411-421 ◽  
Author(s):  
J. M. Adams ◽  
T. V. Clapp ◽  
D. E. Clement
Keyword(s):  
Double Bond ◽  
Liquid Phase ◽  
Ion Exchange ◽  
Acid Catalysis ◽  
Interlayer Space ◽  
Polar Solvent ◽  
Clay Particles ◽  
Interlayer Cations ◽  
Interlayer Region ◽  
Acid Catalysed Reactions

AbstractA preliminary set of ‘rules’ for acid-catalysis by ion-exchanged montmorillonites has been derived from the reaction of alkenes, alcohols and alicyclic acids over such catalysts. It has been shown that: 1. Cr(III) and Fe(III) are the most active interlayer cations. Although Al is also active, the exact procedures used for the ion-exchange and washing steps appear to be critical for giving catalysts of reproducible activity. 2. Below 100°C, the reactions proceed provided they involve tertiary or allylic carbocation intermediates, whereas at 150–180°C reactions involving primary and secondary carbocations are possible. 3. Reactions of carbocations with unsaturated hydrocarbons take place overwhelmingly in the interlayer region of the clay, where the hydrocarbon double bond can be effectively polarized. Reactions of carbocations with polar, oxygenated, species can take place on the surface of the clay particles as well as in the interlayer space. 4. When the acid-catalysed reactions are performed in the liquid phase and involve tertiary carbocations, the most suitable solvents are those which provide miscibility; 1,4-dioxan is especially good. However, when more acid conditions are required for the formation of primary and secondary carbocations a non-polar solvent is more efficacious.

Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

2020 ◽  
Author(s):  
Chang-Sheng Wang ◽  
Sabrina Monaco ◽  
Anh Ngoc Thai ◽  
Md. Shafiqur Rahman ◽  
Chen Wang ◽  
...  
Keyword(s):  
Catalytic System ◽  
Lewis Acid ◽  
Hydrogen Transfer ◽  
Acid Catalysis ◽  
Rate Limiting Step ◽  
Site Selectivity ◽  
Set Up ◽  
Site Selective ◽  
First Time ◽  
Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

Model reactions for the study of hydrogenation and acidic activity of palladium catalysts

1987 ◽  
Vol 52 (8) ◽  
pp. 2019-2027 ◽  
Author(s):  
Libor Červený ◽  
Nguyen Thi Du ◽  
Ivo Paseka
Keyword(s):  
Palladium Catalysts ◽  
Styrene Oxide ◽  
Side Reactions ◽  
Pd Catalysts ◽  
Variable Parameters ◽  
Acid Properties ◽  
Liquid Phase Hydrogenation ◽  
Acid Catalysed Reactions ◽  
Different Content ◽  
Model Reactions

Palladium catalysts have been used to study the hydrogenation of 1-phenyl-2-butene-1-ol which is accompanied by several side reactions considered to be acid-catalysed. Another model reaction studied was dehydration and subsequent hydrogenation or hydrogenolysis of 1-phenyl-1,3-propanediol to 3-phenyl-1-propanol, accompanied by formation of propylbenzene. The dehydration and propylbenzene formation can be again classified as acid-catalysed reactions. Another one is methanolysis of styrene oxide taking place under conditions of liquid phase hydrogenation due to the acid properties of Pd-H systems. Hydrogenation activity of Pd catalysts was tested by hydrogenation of cyclohexene. Sixteen Pd catalysts on different supports and with different content of active component were used, their activity and selectivity was determined and the effect of variable parameters in the synthesis of these catalysts on the activity and selectivity is discussed.

Kinetics and mechanism of cyclization of N-(2-methoxycarbonylphenyl)-N’-methylsulphonamide to 3-methyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide

1991 ◽  
Vol 56 (8) ◽  
pp. 1701-1710 ◽  
Author(s):  
Jaromír Kaválek ◽  
Vladimír Macháček ◽  
Miloš Sedlák ◽  
Vojeslav Štěrba
Keyword(s):  
Potassium Hydroxide ◽  
Acid Catalysis ◽  
Potassium Hydroxide Solution ◽  
Hydroxide Solution ◽  
General Base ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Cyclization Kinetics ◽  
Rate Limiting ◽  
Kinetics Of

The cyclization kinetics of N-(2-methylcarbonylphenyl)-N’-methylsulfonamide (IIb) into 3-methyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide (Ib) has been studied in ethanolamine, morpholine, and butylamine buffers and in potassium hydroxide solution. The cyclization is subject to general base and general acid catalysis. The value of the Bronsted coefficient β is about 0.1, which indicates that splitting off of the proton from negatively charged tetrahedral intermediate represents the rate-limiting and thermodynamically favourable step. In the solutions of potassium hydroxide the cyclization of dianion of the starting ester IIb probably becomes the rate-limiting step.

Sulfur-Mediated Reactions through Sulfonium Salts and Ylides

Synlett ◽  
2021 ◽  
Author(s):  
Pingfan Li
Keyword(s):  
Transition Metal ◽  
Rational Design ◽  
Acid Catalysis ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Bronsted Acid ◽  
Proof Of Concept ◽  
Sulfonium Salts ◽  
Brönsted Acid ◽  
Sulfonium Ylides

AbstractThis Account discusses several new reaction methods developed in our group that utilize sulfur-mediated reactions through sulfonium salts and ylides, highlighting the interplay of rational design and serendipity. Our initial goal was to convert aliphatic C–H bonds into C–C bonds site-selectively, and without the use of transition-metal catalysts. While a proof-of-concept has been achieved, this target is far from being ideally realized. The unexpected discovery of an anti-Markovnikov rearrangement and subsequent studies on difunctionalization of alkynes were much more straightforward, and eventually led to the new possibility of asymmetric N–H insertion of sulfonium ylides through Brønsted acid catalysis.1 Introduction2 Allylic/Propargylic C–H Functionalization3 Anti-Markovnikov Rearrangement4 Difunctionalization of Alkynes5 Asymmetric N–H Insertion of Sulfonium Ylides6 Conclusion

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