Brpnsted base/acid catalysis

This reaction encompasses a number of interesting features (general Brpnsted acid/Bronsted-based catalysis, bifunctional catalysis, enantioselective organoca-talysis, very short hydrogen bonds, similarity to serine protease mechanism, oxyanion hole), and we were able to obtain a complete set of DFT-based data for the entire reaction path, from the starting catalyst-substrate complex to the product complex. 

A different organocatalytic approach to isoquinuclidine molecules has been described based on a cooperative double Brpnsted acid catalysis (Scheme 11.46) [127]. Thus, a proton transfer from the chiral Brpnsted acid to the aromatic imine would occur forming the chiral ion pair A ready to react with the dienol derived from... 

Building upon these concepts, this chapter firstly gives an insight into the modes of action of a selection of non-covalent chiral organocatalysts, employing chiral Brpnsted acid catalysis, chiral Brpnsted base catalysis, and chiral phase-transfer catalysis (PTC). Further sections of this chapter describe two separate case studies that aim to compare and contrast selected covalent and non-covalent strategies for achieving two distinct processes, acyl transfer reactions and asymmetric pericyclic processes. 

Zeolites are crystalline alumino-silicates of formulas Mx/n(Alx+Sii.x)02 yH20 (M" = H+, NH4+, Na+, Fe +, La +...). They are among the most common minerals in nature, and have been extensively used in heterogeneous catalysis since 1970. They present many holes, channels and cavities. Since oxides and zeolites are used extensively in heterogeneous catalysis, it is essential to consider their acid-base properties as defined by their Lewis acid or base and Brpnsted acid or base properties. Indeed, these oxides not only play a role as support, but they also take a very active part in the activation processes. 

During the past decade, Brpnsted acid catalysis has been employed successfully to promote versatile cascade processes, efficiently constructing a huge number of structurally diverse chiral architectures with high optical purity. Based on the deep insights in the active modes and reaction mechanisms, new Brpnsted acid catalysts and... 

Bifunctional catalysts have proven to be very powerful in asymmetric organic transformations [3], It is proposed that these chiral catalysts possess both Brpnsted base and acid character allowing for activation of both electrophile and nucleophile for enantioselective carbon-carbon bond formation [89], Pioneers Jacobsen, Takemoto, Johnston, Li, Wang and Tsogoeva have illustrated the synthetic utility of the bifunctional catalysts in various organic transformations with a class of cyclohexane-diamine derived catalysts (Fig. 6). In general, these catalysts contain a Brpnsted basic tertiary nitrogen, which activates the substrate for asymmetric catalysis, in conjunction with a Brpnsted acid moiety, such as urea or pyridinium proton. 

There are a number of limitations on the Brpnsted relationship. First of aU, the relation holds only for similar types of acids (or bases). For example, carboxylic acids may have a different a values compared to sulfonic acids or phenols. Because charge, and likewise solvation, can greatly influence the reaction rate, deviations of net charge from one catalyst to another can also influence Brpnsted plots. Another limitation on this relationship relates to temperature. Reaction rates and the corresponding dissociation constants for the acids must all be measured at the same temperature (and, most rigorously, in the same solvent). For some systems, this may prove infeasible. A third limitation is that the reaction must indeed be subject to general acid (or base) catalysis. For certain catalysts, deviations from a linear relationship may indicate other modes of action beyond general acid/... 

This type of alkoxylation chemistry cannot be performed with conventional alkali metal hydroxide catalysts because the hydroxide will saponify the triglyceride ester groups under typical alkoxylation reaction conditions. Similar competitive hydrolysis occurs with alternative catalysts such as triflic acid or other Brpnsted acid/base catalysis. Efficient alkoxylation in the absence of significant side reactions requires a coordination catalyst such as the DMC catalyst zinc hexacyano-cobaltate. DMC catalysts have been under development for years [147-150], but have recently begun to gain more commercial implementation. The use of the DMC catalyst in combination with castor oil as an initiator has led to at least two lines of commercial products for the flexible foam market. Lupranol Balance 50 (BASF) and Multranol R-3524 and R-3525 (Bayer) are used for flexible slabstock foams and are produced by the direct alkoxylation of castor oil. 

In the second mechanism, the first and second steps are concerted. In the case of hydrolysis of 2-(p-nitrophenoxy)tetrahydropyran, general acid catalysis was shown470 demonstrating that the substrate is protonated in the rate-determining step (p. 259). Reactions in which a substrate is protonated in the rate-determining step are called A-Se2 reactions.471 However, if protonation of the substrate were all that happens in the slow step, then the proton in the transition state would be expected to lie closer to the weaker base (p. 259). Because the substrate is a much weaker base than water, the proton should be largely transferred. Since the Brpnsted coefficient was found to be 0.5,the proton was actually transferred only... 

With 1-alkoxyallenes as proelectrophiles, the palladium-catalysed asymmetric allylic alkylation proceeds with 1,3-dicarbonyl compounds as pronucleophiles with excellent regioselectivity good enantioselectivity (82-99% ee) was obtained with the Trost lig- and. The pH of the medium proved crucial for the reactivity and selectivity. By using the more acidic Meldrum s acids, the reactions required a co-catalytic amount of a Brpnsted acid, such as CF3CO2H. On the other hand, the less acidic 1,3-diketones failed to react under these conditions but the reaction proved to occur in the presence of the weaker benzoic acid, suggesting the need for general base catalysis. Indeed, a mixture of Et3N and PhCOiH proved to be optimal (93-99% ee). A mechanistic model to rationalize these results has been developed.88... 

The early volumes of the Chemical Society s Quarterly Reviews also contain articles of value for the history of physical organic chemistry Maccoll (on colour and constitution) 401 Bell (on the use of the terms acid and base) 402 Coulson (on molecular orbitals) 403 and Hughes (on steric hindrance).404 The early volumes of Chemical Reviews similarly contain articles of value for the history of physical organic chemistry Gomberg (on free radicals) 405 Holleman (on factors influencing substitution in benzene) 406 Brpnsted (on acid-base catalysis) 407 Ingold (on electronic theories) 408... 

In the proline-based enamine catalysis, proline actually plays a dual role. The amino-group of proline acts as Lewis base, whereas the carboxylic group acts as a Brpnsted acid (Scheme 10). 

Referring to a mechanistic classification of organocatalysts (Seayad and List 2005), currently the two most prominent classes are Brpnsted acid catalysts and Lewis base catalysts. Within the latter class chiral secondary amines (enamine, iminium, dienamine activation for a short review please refer to List 2006) play an important role and can be considered as—by now—already widely extended mimetics of type I aldolases, whereas acylation catalysts, for example, refer to hydrolases or peptidases (Spivey and McDaid 2007). Thiamine-dependent enzymes, a versatile class of C-C bond forming and destructing biocatalysts (Pohl et al. 2002) with their common catalytically active coenzyme thiamine (vitamin Bi), are understood to be the biomimetic roots ofcar-bene catalysis, a further class of nucleophilic, Lewis base catalysis with increasing importance in the last 5 years. 

Many chemical reactions involve a catalyst. A very general definition of a catalyst is a substance that makes a reaction path available with a lower energy of activation. Strictly speaking, a catalyst is not consumed by the reaction, but organic chemists frequently speak of acid-catalyzed or base-catalyzed mechanisms that do lead to overall consumption of the acid or base. Better phrases under these circumstances would be acid promoted or base promoted. Catalysts can also be described as electrophilic or nucleophilic, depending on the catalyst s electronic nature. Catalysis by Lewis acids and Lewis bases can be classified as electrophilic and nucleophilic, respectively. In free-radical reactions, the initiator often plays a key role. An initiator is a substance that can easily generate radical intermediates. Radical reactions often occur by chain mechanisms, and the role of the initiator is to provide the free radicals that start the chain reaction. In this section we discuss some fundamental examples of catalysis with emphasis on proton transfer (Brpnsted acid/base) and Lewis acid catalysis. 

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