Bases carboxylic acid functionality attachment

Although high enantioselectivities are obtained for a wide range of substrates, the stability of the Mn-salen complexes is often a severe problem, and turnover numbers are usually in the range 40-200. More recently, a robust salen catalyst, was introduced by Katsuki and coworkers [77] based on ligand 15 with a carboxylic acid functionality attached to the diamine bridge (Figure 11.4). With this catalyst. 

Various other surface chemistries have been used to attach chemical species to electrode surfaces. For example, Watkins et al. activated the carboxylic acid functionalities on carbon electrodes with thionyl chloride and then reacted this surface with amines [17]. Sagiv and his coworkers have recently invented a clever approach for monolayer-by-monolayer deposition of multilayer films based on organosilane chemistry [18]. Finally, Mallouk et al. have also developed a monolayer-by-monolayer approach for synthesizing well-ordered multilayer films [19]. Because of these interesting new synthetic strategies, covalent attachment of functional groups remains an attractive approach for modifying electrode surfaces. 

The organic resin material is often a styrene divinylbenzene (DVB) copolymer in a network or matrix, to which are attached functional groups such as a sulfonic acid, carboxylic acid, and quaternary ammonium. The nature of these groups determines whether the resin is classified as a strong/weak acid (cation resin) or strong/weak base (anion resin) ion-exchanger. 

CNTs can be processed such as purification based on oxidation, cutting, and activation by forming carboxylic acid and hydroxyl groups on the surface of CNTs, which can further be linked with other biomolecules to realize special function (Ajayan et al., 1994). As shown in Fig. 9.19, ferritin molecules attached to the surface of CNTs via covalent bond, the nanocomposites with ferritin molecules-functionalized CNTs own better mechanical, thermal, and electronic properties... 

In 1989, Rebek and co-workers reported a simple system based on Kemp s triacid that served as a mimic of an enolizing enzyme [86]. This early mimic, however, had the enolizing substrate covalently attached to the triacid skeleton. In addition, the mimic did not possess any oxyanion hole functionalities. However, 2 years later the Rebek group reported a true enolizing catalyst that hosted a carboxylic acid as the oxyanion hole component (Scheme 4.8) [87]. The rate of enolization of the quinuclidone substrate was enhanced by a factor of 10 in the presence of 2.5 mM of the receptor (R = n-Pr). 

Most acid-labile benzyl alcohol linkers suitable for the attachment of carboxylic acids to insoluble supports can also be used to attach aliphatic or aromatic alcohols as ethers. The attachment of alcohols as ethers is less easily accomplished than esterification, and might require the use of strong bases (Williamson ether synthesis [395,552,553]) or acids. These harsh reaction conditions limit the range of additional functional groups that may be present in the alcohol. Some suitable etherification strategies are outlined in Figure 3.31. Etherifications are treated in detail in Section 7.2. 

A cursory glance at the structure of DNA shows that it is composed of hydrogen-bonded units, the purine and pyrimidine bases, attached to sugars that are linked by phosphate groups. There is no chemical reason why the perfectly symmetric phosphates should bind in the orientation that they do. The same problem arises in when a synthetic analogue of a DNA-type replicator is considered. The most useful linkages are imine and peptide bonds. Both require a terminal amine the former results from a reaction with an aldehyde and the latter with an activated carboxylic acid. The problem that occurs is that if these functional groups are present within the same molecule self-polymerization may occur unless a substantial effort is made to avoid this. 

The Kenner sulfonamide-based SC linker 1.27 was supported on PS resin (84) allowing the attachment of carboxylic acids or amino acids to the sulfonamide function. After synthetic elaboration, treatment with diazomethane produces the A-methylacylsulfonamide, which can be cleaved with nucleophiles such as 0.5 N NHs-dioxane or hydrazine-MeOH, 0.5 N NaOH, releasing amides, hydrazides, or carboxylic acids, respectively. A modification using iodoacetonitrile produces the more labile A-cyanomethyl derivative, which can be cleaved completely with stoichiometric amounts of amines to release the corresponding amides into solution. 

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