Lewis reactions

Comparison of Bronsted reaction 4.48 with Lewis reaction 4.49 shows that the Lewis theory is more generally applicable, but its interpretation is different in terms of the definition of acids and complexes. In fact, the Lewis theory is valid for all acid-base reactions (cf., eqns. 4.39 and 4.40). 

This is both a Bronsted acid-base reaction and a Lewis acid-base reaction. The Bronsted reaction involves the transfer of protons ftom HF molecules to O" ions, whereas the Lewis reaction involves complex fonnation between Si(IV) centre and F ions. 

L. B. Davin N. G. Lewis, Reaction tissue formation and stem tensile modulus properties in wild type and p-coumarate-3-hydroxylase downregulated lines of alfalfa, Medicago sativa (Fabaceae), pp 912-925, Copyright 2007, with permission from the Botanical Society of America (g). 

Malachite and aurichalcite cannot be distinguished by using only precipitation reactions and Bronsted-Lowry add-base reactions. Another type of acid-base reaction, the Lewis reaction (reaction category 3), is necessary. Zinc ion will react with hydroxide ion to form insoluble zinc hydroxide (solubility rule 4), which will then react with excess hydroxide ion as a Lewis add to form the soluble Lewis adduct Zn(OH)4 Although the copper ion will react with hydroxide ion to form insoluble Cu(OH)2, this hydroxide does not ad as a Lewis acid and will not dissolve in excess hydroxide ion. 

The IR spectral data of the organic component of TPB-clay reactions on different Fe-containing clays indirectly infers the role of stmctural Fe(III) in the Lewis reaction pathway. Although the octahedral Fe-OH deformation bands in the IR spectra of Fe-containing smectites (data not shown) support the hypothesis of structural Fe reduction, the relevant bands are ill-resolved and difficult to interpret analytically. The application... 

Eventually, the left reaction implies that partial charge transfer through Lewis acids and bases occurs, while the right reaction states for Ihe complete charge transfer redox process. In these conditions, the exchange of electrons between the radicalic extremes of Lewis reaction arises through... 

The most widely used reactions are those of electrophilic substitution, and under controlled conditions a maximum of three substituting groups, e.g. -NO2 (in the 1,3,5 positions) can be introduced by a nitric acid/sul-phuric acid mixture. Hot cone, sulphuric acid gives sulphonalion whilst halogens and a Lewis acid catalyst allow, e.g., chlorination or brom-ination. Other methods are required for introducing fluorine and iodine atoms. Benzene undergoes the Friedel-Crafts reaction. ... 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Szundi I, Lewis J W and Kliger D S 1997 Deriving reaction mechanisms from kinetic spectroscopy. Application to late rhodopsin intermediates Blophys. J. 73 688-702... 

When carbon forms four covalent bonds with halogen atoms the second quantum level on the carbon is completely filled with electrons. Most of the reactions of the Group IV tetrahalides require initial donation by a Lewis base (p. 91) (e.g. water, ammonia) which attaches initially to the tetrahalide by donation of its electron pair. Hence, although the calculated free energy of a reaction may indicate that the reaction is energetically favourable, the reaction may still not proceed. Thus we find that the tetrahalides of carbon... 

Ene reaction with aldehydes is catalyzed by Lewis Acids (Et2AlCl)... 

Lewis acids can greatly effect the endo/exo ratio of IDA reactions especially when the olefin portion is E. The effects for Z-oIefins is much more subtle... 

This chapter introduces the experimental work described in the following chapters. Some mechanistic aspects of the Diels-Alder reaction and Lewis-acid catalysis thereof are discussed. This chapter presents a critical survey of the literature on solvent ejfects on Diels-Alder reactions, with particular emphasis on the intriguing properties of water in connection with their effect on rate and selectivity. Similarly, the ejfects of water on Lewis acid - Lewis base interactions are discussed. Finally the aims of this thesis are outlined. 

Lewis-acid catalysis of Diels-Alder reactions... 

The regioselectivity benefits from the increased polarisation of the alkene moiety, reflected in the increased difference in the orbital coefficients on carbon 1 and 2. The increase in endo-exo selectivity is a result of an increased secondary orbital interaction that can be attributed to the increased orbital coefficient on the carbonyl carbon ". Also increased dipolar interactions, as a result of an increased polarisation, will contribute. Interestingly, Yamamoto has demonstrated that by usirg a very bulky catalyst the endo-pathway can be blocked and an excess of exo product can be obtained The increased di as tereo facial selectivity has been attributed to a more compact transition state for the catalysed reaction as a result of more efficient primary and secondary orbital interactions as well as conformational changes in the complexed dienophile" . Calculations show that, with the polarisation of the dienophile, the extent of asynchronicity in the activated complex increases . Some authors even report a zwitteriorric character of the activated complex of the Lewis-acid catalysed reaction " . Currently, Lewis-acid catalysis of Diels-Alder reactions is everyday practice in synthetic organic chemistry. 

Unfortunately, the number of mechanistic studies in this field stands in no proportion to its versatility" . Thermodynamic analysis revealed that the beneficial effect of Lewis-acids on the rate of the Diels-Alder reaction can be primarily ascribed to a reduction of the enthalpy of activation ( AAH = 30-50 kJ/mole) leaving the activation entropy essentially unchanged (TAAS = 0-10 kJ/mol)" . Solvent effects on Lewis-acid catalysed Diels-Alder reactions have received very little attention. A change in solvent affects mainly the coordination step rather than the actual Diels-Alder reaction. Donating solvents severely impede catalysis . This observation justifies the widespread use of inert solvents such as dichloromethane and chloroform for synthetic applications of Lewis-acid catalysed Diels-Alder reactions. 

Studies on solvent effects on the endo-exo selectivity of Diels-Alder reactions have revealed the importance of hydrogen bonding interactions besides the already mentioned solvophobic interactions and polarity effects. Further evidence of the significance of the former interactions comes from computer simulations" and the analogy with Lewis-acid catalysis which is known to enhance dramatically the endo-exo selectivity (Section 1.2.4). 

In a Lewis-acid catalysed Diels-Alder reaction, the first step is coordination of the catalyst to a Lewis-basic site of the reactant. In a typical catalysed Diels-Alder reaction, the carbonyl oxygen of the dienophile coordinates to the Lewis acid. The most common solvents for these processes are inert apolar liquids such as dichloromethane or benzene. Protic solvents, and water in particular, are avoided because of their strong interactions wifti the catalyst and the reacting system. Interestingly, for other catalysed reactions such as hydroformylations the same solvents do not give problems. This paradox is a result of the difference in hardness of the reactants and the catalyst involved... 

The most effective Lewis-acid catalysts for the Diels-Alder reaction are hard cations. Not surprisingly, they coordinate to hard nuclei on the reacting system, typically oxygen atoms. Consequently, hard solvents are likely to affect these interactions significantly. Table 1.4 shows a selection of some solvents ranked according to their softness. Note that water is one of the hardest... 

In summary, water is clearly an extremely bad solvent for coordination of a hard Lewis acid to a hard Lewis base. Hence, catalysis of Diels-Alder reactions in water is expected to be difficult due to the relative inefficiency of the interactions between the Diels-Alder reactants and the Lewis-acid catalyst in this medium. 

A combination of the promoting effects of Lewis acids and water is a logical next step. However, to say the least, water has not been a very popular medium for Lewis-acid catalysed Diels-Alder reactions, which is not surprising since water molecules interact strongly with Lewis-acidic and the Lewis-basic atoms of the reacting system. In 1994, when the research described in this thesis was initiated, only one example of Lewis-acid catalysis of a Diels-Alder reaction in water was published Lubineau and co-workers employed lanthanide triflates as a catalyst for the Diels-Alder reaction of glyoxylate to a relatively unreactive diene . No comparison was made between the process in water and in organic solvents. 

In view of the remarkable effects that water can exert on the uncatalysed Diels-Alder reaction, there might well be a similar effect on the rate and the selectivity of the Lewis-acid catalysed process. At the same time, coordination of a Lewis-acid to a Diels-Alder reagent is likely to overcome the... 

What is the effect of water on the rate and selectivity of the Lewis-acid catalysed Diels-Alder reaction, when compared to oiganic solvents Do hydrogen bonding and hydrophobic interactions also influence the Lewis-acid catalysed process Answers to these questions will be provided in Chapter 2. 

What is the influence of ligands on the Lewis acid on the rate and selectivity of the Diels-Alder reaction If enantioselectivity can be induced in water, how does it compare to other solvents Chapter 3 deals with these topics. 

What is the scope of Lewis-acid catalysis of Diels-Alder reactions in water An approach of extending the scope by making use of a temporary secondary coordination site is described in Chapter 4. 

What is the effect of micelles on the aqueous Diels-Alder reaction Can micellar catalysis be combined with Lewis-acid catalysis In Chapter 5 these aspects will discussed. 

Appreciating the beneficial influences of water and Lewis acids on the Diels-Alder reaction and understanding their origin, one may ask what would be the result of a combination of these two effects. If they would be additive, huge accelerations can be envisaged. But may one really expect this How does water influence the Lewis-acid catalysed reaction, and what is the influence of the Lewis acid on the enforced hydrophobic interaction and the hydrogen bonding effect These are the questions that are addressed in this chapter. 

In order to be able to provide answers to these questions, a Diels-Alder reaction is required that is subject to Lewis-acid catalysis in aqueous media. Finding such a reaction was not an easy task. Fortunately the literature on other Lewis-acid catalysed organic reactions in water was helpful to some extent... 

Lewis-acid catalysis of organic reactions in aqueous solutions ... 

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