Supported reagents surfaces

It years, there has been a considerable growth of interest in the catalysis of organic IS by inorganic reagents supported on high surface areas, Envirocat, a new family of supported reagents, which exhibits both Bronstead and Lev/is acid character, are ideal for environmentally friendly chemistry. These reagents are non-toxic powders that can be easily... 

Viewed in conjunction with the solid-like, nonvolatile nature of ionic liquids, it is apparent that TSILs can be thought of as liquid versions of solid-supported reagents. Unlike solid-supported reagents, however, TSILs possess the added advantages of kinetic mobility of the grafted functionality and an enormous operational surface area (Figure 2.3-1). It is this combination of features that makes TSILs an aspect of ionic liquids chemistry that is poised for explosive growth. 

Heterogeneous reactions facilitated by supported reagents on inorganic oxide surfaces have received attention in recent years, both in the laboratory as well as in industry. Although the first description of the surface-mediated chemical transformation dates back to 1924 [13], it was not until almost half a century later that the technique received extensive attention with the appearance of several reviews, books and account articles [14—22],... 

The quest for a solvent-free deprotection procedure has led to the use of relatively benign reagent, ammonium persulfate on silica, for regeneration of carbonyl compounds (Scheme 6.10) [48]. Neat oximes are simply mixed with solid supported reagent and the contents are irradiated in a MW oven to regenerate free aldehydes or ketones in a process that is applicable to both, aldoximes and ketoximes. The critical role of surface needs to be emphasized since the same reagent supported on clay surface delivers predominantly the Beckmann rearrangement products, the amides [49]. 

Methods like these have made polymer-supported synthesis so valuable a method that it is now being developed for many reactions old and new. A recent (1999) issue of the journal Perkin Transactions 1 reported two syntheses of natural products in which every step was carried out using a polymer-supported reagent. Polymers are vital to us in everyday life in a multitude of ways and new polymers are being invented all the time. We have done no more than scratch the surface of this subject and you should turn to more specialized books if you want to go further. 

The actual chemical nature of the support material may be and often is of direct importance to its usefulness as a support material.15 Silicas can react with small nucleophiles such as F-, OH- and CN. Thus, silica-supported fluorides are inactive, both as nucleophilic fluorinating agents and as bases. Similarly, silicas are not effective support materials for cyanides due to the formation of strong Si-CN bonds. For different reasons, an acidic clay would not be a suitable support for cyanides, due to the possible formation of toxic HCN. Charcoal is the most effective support material for stabilising Cu(I), probably due to its aromatic character.16 For many chemisorbed supported reagent catalysts, silicas are preferred since they give relatively strong surface bonds. However, Si-O-C bonds are hydrolytically vunerable and direct Si-C bonds are preferred.17... 

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