Lewis acidity tuning

Scheme 4 Synthesis of block copolymers via capping reaction of living PIB with DPE, followed by Lewis acidity tuning and sequential monomer addition...

Evans et al. reported that the bis(imine)-copper (II) complex 25, prepared from chiral bis(imine) ligand and Cu(OTf)2, is also an effective chiral Lewis acid catalyst [34] (Scheme 1.44, Table 1.18). By tuning the aryl imine moiety, the bis(2,6-dichlor-ophenylimine) derivative was found to be suitable. Although the endojexo selectivity for 3-alkenoyloxazolidinones is low, significant improvement is achieved with the thiazolidine-2-thione analogs, for which both dienophile reactivity and endojexo selectivity are enhanced. 

Buchanan and co-workers studied the behavior of various aromatic compounds in antimony(III) molten salts [30]. These salts can act both as mild Lewis acids and allow redox reactions to take place. The Lewis acidity of the melt can be tuned by controlling the concentration of [SbCl2]. Basic melts are formed by addition of a few mol % of a chloride donor such as KCl, whereas acidic melts are formed by addition of chloride acceptors such as AICI3 (Scheme 5.1-11). 

The combination of metal tuning and double stereodifferentiation helps to prepare chelation and nonchelation products in the imine series7. In the case of an alkoxy substituent adjacent to the aldimino, the chelation product 10 is predominantly obtained with allylmagnesium chloride, chloromagnesium allyltriethylaluminate or allylzinc bromide, while the use of allyl-boronates or allyltitanium triisopropoxide, which lack the requisite Lewis acidity for chelation, gives 11 with good Cram selectivity. 

In analogy to its complexes with nitrosyl cation (as described above), benzene can form donor-acceptor adducts with a variety of metallic and non-metallic Lewis acids. These lead to materials with novel optical and electrical properties that can be tuned through substituents on the aromatic ring. 

In order to quantify the transition metal ion concentration, Jones et al. [107] developed a highly sensitive fluorescent chemosensor in the form of dialkoxy-phenyleneethynylene-thiophene copolymers 68/69. The PAEs were functionalized on the thiophene unit with terpyridine (68), and included 2,2 -bipyridine (69) as a Lewis acid receptor. The terpyridine polymers [108] were found to respond quantitatively to transition metal ions at concentrations as low as 4x10 M (NP, Hg, Cr ", and Co " ). The additionally used bpy-PAE demonstrates that variation in the chelation at the receptor site is an important variable in tuning selectivity. The observed dynamic quenching mechanism, combined with the solubility of this material, provides the opportunity to extend these initial investigations to thin solid films for use in real-time monitoring applications. 

Snapper and Hoveyda reported a catalytic enantioselective Strecker reaction of aldimines using peptide-based chiral titanium complex [Eq. (13.11)]. Rapid and combinatorial tuning of the catalyst structure is possible in their approach. Based on kinetic studies, bifunctional transition state model 24 was proposed, in which titanium acts as a Lewis acid to activate an imine and an amide carbonyl oxygen acts as a Bronsted base to deprotonate HCN. Related catalyst is also effective in an enantioselective epoxide opening by cyanide "... 

Until recently the most popular method in asymmetric catalysis was the application of metal complexes. This is not surprising, since the use of different metals, ligands and oxidation states makes it possible to tune selectivity and perform asymmetric induction very easily. Thus, the concept of asymmetric catalysis has become almost synonymous with the use of metals coordinated by chiral ligands [1,2]. In many examples the metal is a Lewis acid [3]. 

Some ionic liquids have tunable Lewis acidities and basicities. The tuning can be achieved simply by varying the anion fraction in the overall ionic liquid composition. In some cases, Bronsted acidity can also be introduced into stable ionic liquids. Many publications show the broad applicability of acidic or basic ionic liquid media in catalysis replacing corrosive liquids and solid catalysts. 

The second step in the hexose synthesis was the aldol condensation of 4 with another a-hetero aldehyde derivative S. By tuning the Lewis acid and the solvent, three of the four possible diastereomeric products could be selectively prepared. a-Amino and a-thio aldehydes worked well also, leading to 9 and 10 respectively. 

Alkyl spacers thus offer the opportunity to finely tune the interplay between the antagonist sites of ambiphilic compounds. The proximity of the phosphine and borane moieties, and thus the possible formation of intramolecular P-B interaction depend on the number of carbon atoms present in the backbone and on the Lewis acidity of the borane. Conformational considerations may also play an important role as for the ethylene-bridged systems. 

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