Lewis adds

Several alternative attempts have been made to quantify Lewis-acid Lewis-base interaction. In view of the HSAB theory, the applicability of a scale which describes Lewis acidity with only one parameter will be unavoidably restricted to a narrow range of struchirally related Lewis bases. The use of more than one parameter results in relationships with a more general validity ". However, a quantitative prediction of the gas-phase stabilities of Lewis-acid Lewis-base complexes is still difficult. Hence the interpretation, not to mention the prediction, of solvent effects on Lewis-add Lewis-base interactions remains largely speculative. 

Fortunately, azachalcone derivatives (2.4a-g, Scheme 2.4) turned out to be extremely suitable dienophiles for Lewis-add catalysed Diels-Alder reactions with cyclopentadiene (2.5). This reaction is outlined in Scheme 2.4 and a large part of this thesis will be devoted to the mechanistic details of this process. The presence of a chromophore in 2.4 allows kinetic studies as well as complexation studies by means of UV-vis spectroscopy. Furthermore, the reactivity of 2.4 is such that also the... 

Table 2.7. Hammett p-values for complexation of 2.4a-e to different Lewis-adds and for rate constants (kcat) of the Diels-Alder reaction of 2.4a-e with 2.5 catalysed by different Lewis-acids in water at 2.00 M ionic strength at 25°C.

When exclusively considering Lewis-add catalysis, the literature on ligand effects can be divided into studies describing quantitatively the effect of ligands on rates and equilibria of the individual steps in the catalytic cycle on one hand, and studies focused on the enantioselectivity of the reaction on the other. Interestingly, in the majority of the former investigations, aqueous media are employed. 

Literature claims of Lewis-acid catalysis of Diels-Alder reactions in water At the time of the printing of this thesis eight reports describe Lewis-acid catalysis of Diels-Alder reactions in water. This small number indicates that Lewis-add catalysis in aqueous media suffers not only from unpopularity, but also from an intrinsic disadvantage. Three of these reports originate... 

Inspired by the work of Burk and Feaster ) we attempted to use (2-pyridyl)hydrazine (4.36) as a coordinating auxiliary (Scheme 4.10). Hydrazines generally react effidently with ketones and aldehydes. Hence, if satisfactory activation of the dienophile can be achieved through coordination of a Lewis acid to the (2-pyridyl)hydrazone moiety in water. Lewis-add catalysis of a large class of ketone- and aldehyde-activated dienophiles is antidpated Subsequent conversion of the hydrazone group into an amine functionality has been reported previously by Burk and Feaster ... 

In this section the influence of micelles of cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS) and dodecyl heptaoxyethylene ether (C12E7) on the Diels-Alder reaction of 5.1a-g with 5.2 in the absence of Lewis-add catalysts is described (see Scheme 5.1). Note that the dienophiles can be divided into nonionic (5.1a-e), anionic (5.If) and cationic (5.1g) species. A comparison of the effect of nonionic (C12E7), anionic (SDS) and cationic (CTAB) micelles on the rates of their reaction with 5.2 will assess of the importance of electrostatic interactions in micellar catalysis or inhibition. 

Of all the work described in this thesis, this discovery is probably the most significant. Given the fact that the arene - arene interactions underlying the observed enantioselectivity of ftie Diels-Alder reactions described in Chapter 3 are also encountered in other organic reactions, we infer that, in the near future, the beneficial influence of water on enantioselectivity can also be extended to these transformations. Moreover, the fact that water can now be used as a solvent for enantioselective Lewis-add catalysed reactions facilitates mechanistic studies of these processes, because the number of equilibria that need to be considered is reduced Furthermore, knowledge and techniques from aqueous coordination chemistry can now be used directly in enantioselective catalysis. 

Analogously, water is extremely efficient in weakening hard Lewis add - hard Lewis base interactions. Consequently, when aiming at catalysis by hard Lewis adds, the inefficiency of the interaction between the catalyst and the substrate is a serious problem. Strangely enough, this characteristic of water is not recognised by many researchers working with hard Lewis acids in... 

This thesis describes a study of catalysis of Diels-Alder reactions in water. No studies in this field had been reported at the start of the research, despite the well known beneficial effects of acpieous solvents as well as of Lewis-add catalysts on rate and endo-exo selectivity of Diels-Alder reactions in organic solvents. We envisaged that a combination of these two effects might well result in extremely large rate enhancements and improvements of the endo-exo selectivity. 

The rate of the Lewis-acid catalysed Diels-Alder reaction in water has been compared to that in other solvents. The results demonstrate that the expected beneficial effect of water on the Lewis-acid catalysed reaction is indeed present. However, the water-induced acceleration of the Lewis-add catalysed reaction is not as pronounced as the corresponding effect on the uncatalysed reaction. The two effects that underlie the beneficial influence of water on the uncatalysed Diels-Alder reaction, enforced hydrophobic interactions and enhanced hydrogen bonding of water to the carbonyl moiety of 1 in the activated complex, are likely to be diminished in the Lewis-acid catalysed process. Upon coordination of the Lewis-acid catalyst to the carbonyl group of the dienophile, the catalyst takes over from the hydrogen bonds an important part of the activating influence. Also the influence of enforced hydrophobic interactions is expected to be significantly reduced in the Lewis-acid catalysed Diels-Alder reaction. Obviously, the presence of the hydrophilic Lewis-acid diminished the nonpolar character of 1 in the initial state. 

CLOKE - WILSON Cyclopropylkelone Rearrangement Rearrangement o( cyclopropyl ketones or imines to dihydnofurans or dihydropyrroles, thermally, photochemically, or by Lewis adds... 

GATTERMAN - KOCH Cartionylation Synthesis of aromatic aldehydes or ketones using cyanide salts or CO - HCI and Lewis adds. 

On tlie basis of tliis Lotidusioti and on NMR studies of Lomplexes of 17b witli Lewis adds, a transition state model to explain tlie observed sdectivity was proposed. Tliis involved initial Lomplexation of a cuprate litliium ion to tlie tliree different betetoatoms in tlie substrate, followed by fotniation of a d-E complexation... 

Alkyladon of ketene sdyl acetals v/ith nltroalkenes has several hirutatrons such as modest yield, lack of generality, and inconveniently low reacdon temperatures. Tucker and coworkers have found that sterically encumbered Lev/is acids such as MAD give better results than other Lewis adds fEq. 4.64. ... 

Yamamoto H., Yanagisawa A., Ishihara K., Salto S. Designer Lewis Adds for Selective Organic Synthesis Pure Appl. Chem. 1998 70 1507-1512 Keywords Lewis-acid reagents... 

Wada E., Yasuoka H., Pei W., Chin U., Kanemasa S. Lewis Add-Catalyzed Stereoselective Hetero Diels-Alder Reactions of (E)-l-Phenylsulfonyl-3-Alken-2-Ones With Vinyl Ethers. Synthetically Equivalent to Stereoselective Michael Type... 

The weaker Lewis add TMSOTf 20 as catalyst gives, after 2 h at 0°C in CH2CI2, a 20 80 mixture of 805 and 806 in only 23% yield (Scheme 6.8). But this yield will probably increase either on longer reaction time at 0°C or on shorter reaction time at 25 °C On replacing one of the methyl groups in 804 by an acetylene substituent the resulting enyne adds allyltrimethylsilane 82 or anisole in the presence of TMSOTf 20 to give allenes [18]. Substituted allyltrimethylsilanes such as 808 react with the allylic silylether 807 after 70 h at 25 °C in 62% yield to a 41 59 mixture of 809 and 810 as well as 7 [17]. Closely related additions of 82 to allylic ethers or O-acetates are discussed in Refs. 17a-c. 

When H-EDTA-MOR was exposed to 0.3 kPa of NH3 at 473 K and evacuated at 473 K (Figure 6E), only protonated ammonia (NH4 ) was observed. The NH4" deformation band builds up at 1443 cm- together with a small amount of coordinated NH3 bonds (deformation) that attached to Lewis add sites at 1624 cm L... 

The major addic sites on H-MOR are Bronsted sites determined by pyridine adsorption studies above 80 % of addic sites are Br0nsted sites and the rest are Lewis add sites [4,5]. After adsorption of NH3, 0.3 kPa of EA are admitted on H-EDTA-MOR at 473 K (Figure 6F) adsorbed NH3 is easily replaced by EA to produce deformation bands of NH3+ (1597 cm-i, 1497 cm-t), CH2 (1460 cm-i). This spectrum is quite the same as the spectrum in Figure 6A. The results suggest that adsorption of EA is much stronger than that of NH3. When adsorbed EA is heated up to 573 K (Figure 6G-6H), the spectra are almost the same as the spectra in Figure 6B and 6C. 

The recovery of the Lewis add sites and the decrease in the protonic acid sites to the original values by outgassing gas phase hydrogen are rather slow and require a high temperature. The addition of Pt/Si02 did not affect much the restoration of Ae Lewis add sites of H-ZSM-5 by outgassing gas phase hydrogen. 

Although Lewis and Bronsted bases comprise the same species, the same is not true of their acids. Lewis acids include bare metal cations, while Bronsted-Lowry acids do not. Also, Bell (1973) and Day Selbin (1969) have pointed out that Bronsted or protonic acids fit awkwardly into the Lewis definition. Protonic acids cannot accept an electron pair as is required in the Lewis definition, and a typical Lewis protonic add appears to be an adduct between a base and the add (Luder, 1940 Kolthoff, 1944). Thus, a protonic acid can only be regarded as a Lewis add in the sense that its reaction with a base involves the transient formation of an unstable hydrogen bond adduct. For this reason, advocates of the Lewis theory have sometimes termed protonic adds secondary acids (Bell, 1973). This is an unfortunate term for the traditional adds. 

Gabbai, F.P., Schier, A., Riede, J. and Tschrnkl, M.T. (1999) Micropore decoration with bidentate lewis adds spontaneous assembly of l,2-Bis(chloromercurio) tetrafluorobenzene. Angewandte Chemie International Edition, 38, 3547. 

---