Cross-linked polymer supports alternatives

Chemistry on soluble polymer matrices has recently emerged as a viable alternative to solid-phase organic synthesis (SPOS) involving insoluble cross-linked polymer supports. Separation of the functionalized matrix is achieved by solvent or heat precipitation, membrane filtration, or size-exclusion chromatography. Suitable soluble polymers for liquid phase synthesis should be crystalline at room temperature, with functional groups on terminal ends or side chains, but must not be not cross-linked they are therefore soluble in several organic solvents. 

Possible alternatives to cross-linked polymer supports are soluble and colloidal polymers. They would require large scale ultrafiltration for industrial use. Although ultrafiltration is not yet economical for desalination of seawater, it might be for a separation of a more expensive product. One example is the catalytic partial hydrogenation of soybean oil (361 with soluble polymer-bound transition metal complexes. Solid inorganic supports such as silica gel and alumina are usually not subject to these physical attrition and filtration problems. 

Various polymer-supported hydrides have been applied successfully to reductions of both carbonyl and olefin groups. Rajasree and Devaky13 describe a cross-linked polystyrene-supported ethylenediamine borane reagent for the selective reduction of aldehydes in the presence of ketones (entry 9). This borane reagent is easily prepared and can be recycled after completion of the reaction. This is a practical alternative to standard borane reagents such as diborane, borane-amine, or borane-sulfide complexes. 

In arrays of closely packed nucleosomes composed of all four core histones, strands of H2A-H2B dimers could be incorporated in the grooves between the two H3-H4 strands, producing a four-stranded polymer. Alternatively, they could bind to the H3-H4 double-stranded fiber to give an octamer of the histones per nucleosome. This latter model is supported by the photochemical cross-linking of histones to DNA which have shown that within the nucleosome core the four core histones are not equivalently positioned with respect to... 

As an alternative, stable high-coverage nonpolar RPC sorbents phases have been prepared by cross-linking hydrophobic polymers at the silica surface, either via free radical 143 or condensation 101 polymerization chemistry. In this case, the underlying silica becomes partly protected from hydrolytic degradation due to the presence of the hydrophobic polymer film coating that effectively shields the support material. Similar procedures have been employed to chemically modify the surface of other support materials, such as porous zirconia, titania, or alumina, to further impart resistance to degradation when alkaline mobile-phase conditions are employed. Porous polystyrene-divinylbenzene sorbents, be-... 

The alternative strategy for heterogenization has been pursued by Blechert and co-workers, for a polymer-supported olefin metathesis catalyst. A polymer-anchored carbene precursor was prepared by coupling an alkoxide to a cross-linked polystyrene Merrifield-type resin. Subsequently, the desired polymer-bound carbene complex was formed by thermolytically induced elimination of ferf-butanol while heating the precursor resin in the presence of the desired transition metal fragment (Scheme 8.30). 

Alternatively, boranes can be prepared in solution and then coupled with support-bound carbon electrophiles. The Suzuki coupling of alkylboranes, generated in situ from 9-BBN and alkenes, with brominated cross-linked polystyrene has been used to link substituted alkyl chains directly to the polymer (Entry 4, Table 5.3). Alkylboranes have also been used to alkylate polystyrene-bound aryl iodides (Entries 3 and 5, Table 5.3). 

PAMAM]. The final step of this functionalization relied on activation and cross-linking of attached dendrimers with a homobifunctional spacer (DSG or PDITC). Alternatively, after attachment of dendrimers to the surface, glutaric anhydride activated with V-h ydrox vsucc i n i m i de can be used. This surface modification yields a thin, chemically reactive polymer film, which is covalently attached to the glass support and can be directly used for the covalent attachment of amino-modified components, such as DNA or peptides (Fig. 14.2b). 

To overcome such limitations, Imura et al. covered the surface of a silica gel with sulfonated cross-linked polystyrene [5]. After adsorption of styrene, divinyl-benzene, and r-butyl peroxide and subsequent free-radical polymerization, the acid groups are introduced via classical sulfonation. Control of the thickness of the crosslinked polymer layer on the surface is essential to prevent pore clogging. This sulfonated polystyrene-Si02 hybrid material preserves a large specific surface area, with a typical ion-exchange capacity of 1.8 meq g. Alternatively, a sulfonated layer can be deposited on silica by copolymerization of silica-supported methacrylate and potassium p-styrene sulfonate [6]. 

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