Resins, cross-linked polystyrene support

Devaky and Rajasree have reported the production of a polymer-bound ethylenediamine-borane reagent (63) (Fig. 41) for use as a reducing agent for the reduction of aldehydes.87 The polymeric reagent was derived from a Merrifield resin and a 1,6-hexanediol diacrylate-cross-linked polystyrene resin (HDODA-PS). The borane reagent was incorporated in the polymer support by complexation with sodium borohydride. When this reducing agent was used in the competitive reduction of a 1 1 molar mixture of benzaldehyde and acetophenone, benzaldehyde was found to be selectively reduced to benzyl alcohol. 

Numerous resin supports are commercially available for solid-phase synthesis and some allow the acquisition of quite reasonable quality spectra of compounds bonded to them - and some don t. The resins to avoid (if you intend trying to monitor your reactions by MAS-NMR) are any that are based purely on cross-linked polystyrene. These are too rigid and afford little or no mobility to any bound compound. These resins are relatively cheap and have high specific loadings but will give very poor spectra even in a MAS probe. We see little point in running spectra of compounds on these resins as the quality of the spectra make them virtually useless - and perhaps worse - potentially misleading. 

Use of benzene suspensions containing a neutral rhodium(I)-DIOP complex supported on a cross-linked polystyrene (50) (cf. 13 in Section III,A) for hydrogenation of a-ethylstyrene (to 1.5% ee) and methyl atro-pate (2.5% ee) was less effective than the homogeneous system, as the ethanol cosolvent required for substrate solubility caused a collapse of the resin (296). 

Reversed-phase chromatography employs a nonpolar stationary phase and a polar aqueous-organic mobile phase. The stationary phase may be a nonpolar ligand, such as an alkyl hydrocarbon, bonded to a support matrix such as microparticulate silica, or it may be a microparticulate polymeric resin such as cross-linked polystyrene-divinylbenzene. The mobile phase is typically a binary mixture of a weak solvent, such as water or an aqueous buffer, and a strong solvent such as acetonitrile or a short-chain alcohol. Retention is modulated by changing the relative proportion of the weak and strong solvents. Additives may be incorporated into the mobile phase to modulate chromatographic selectivity, to suppress undesirable interactions of the analyte with the matrix, or to promote analyte solubility or stability. 

A key element in the original Merriheld procedure of solid-phase synthesis is the solid support system. That system consists of two parts a resin head and a. linker, an organic compound used to join the hrst amino acid to the resin head. The resin beads used by Merriheld are small spherical objects made of cross-linked polystyrene. This material consists primarily of the polymer polystyrene whose linear molecules are linked to each other at various positions by the addition of divinylhenzene (CH2 = CHCgH jCH =CH2). The hnal cross-linked material is relatively rigid, with enough hexihility to permit... 

Aiming at easier workup conditions, immobilization of several transition metal catalysts, which show activity for the epoxidation of allylic alcohols, on polymer support has been investigated. For example, Suzuki and coworkers incorporated an oxo-vanadium ion into cross-linked polystyrene resins functionalized with iminodiacetic acid or diethylenetri-amine derivatives (Scheme 57), which afforded a heterogeneous catalyst that can promote... 

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). 

The oxidative hydrolysis and acetylation of olefins in the presence of palladium(II) salts are well-established as commercial routes to acetaldehyde and vinylacetate (46). Both processes have been investigated using supported catalysts. The oxidative hydrolysis has been briefly studied using palladium(ll) chloride supported on a cross-linked polystyrene resin containing cyano groups (64). Oxidative acetylation was effected using palladium(II) chloride supported on phosphinated silica (5). 

Typical solid supports used in organic syntheses are resin beads formed from cross-linked polystyrene (PS 40-150 pm diameter), polystyrene-... 

Low cross-linked polystyrene resins (1% divinylbenzene) is probably the most popular solid support. These resins swell to 2-6 times their original volume depending on the solvent used. Swollen resin, after removal of solvent and without excessive drying, remains in a rubbery state and can be easily flattened for FTIR study in the transmission mode. The support-bound compound should be washed free of reagent and solvent. 

Another kind of solid support that has gained more popularity is the surface-modified polypropylene, such as the Multipin crown and Microtubes. Reaction 3 was carried out on lightly and highly cross-linked polystyrene resins (1 % and >20% divinylbenzene, respectively), poly sty rene-PEG resin, and a surface-functionalized Microtube reactor.12 The reaction kinetics on these supports is compared in Figures 7.4 and 7.5. The reaction on the highly cross-linked polystyrene resin was shown to be slower than on other supports and the reaction on Microtube was faster than on polystyrene resins. 

Cross-linked polystyrene can be functionalized in many ways [38 41]. Those functionalized resins that are frequently used as supports for solid-phase synthesis are commercially available, and their preparation will be mentioned only in brief here. 

Support-bound triazenes, which can be prepared from resin-bound secondary aliphatic amines and aromatic diazonium salts [455], undergo cleavage upon treatment with acids, leading to regeneration of the aromatic diazonium salts. In cross-linked polystyrene, these decompose to yield nitrogen and, preferentially, radical-derived products. If the acidolysis of polystyrene-bound triazenes is conducted in the presence of hydrogen-atom donors (e.g. THF), unsubstituted arenes can be obtained (Entries 8 and 9, Table 3.47). In the presence of alkenes or alkynes and Pd(OAc)2, the initially formed diazonium salts undergo Heck reaction to yield vinylated or alkynylated arenes (Entry 10, Table 3.47). Similarly, unsubstituted arenes can be obtained by oxida-... 

Thioethers have also been prepared on cross-linked polystyrene by radical addition of thiols to support-bound alkenes and by reaction of support-bound carbon radicals (generated by addition of carbon radicals to resin-bound acrylates) with esters of l-hydroxy-l,2-dihydro-2-pyridinethione ( Barton esters Entry 6, Table 8.5). Additional methods include the reaction of metallated supports with symmetric disulfides (Entries 7-9, Table 8.5) and the alkylation of polystyrene-bound, a-lithiated thioani-sole [65],... 

Support-bound 1,2-diamines can be readily converted into imidazolidinones by treatment with carbonyl diimidazole [128,129]. The required diamines have been prepared on cross-linked polystyrene by reduction of peptides bound to MBHA resin with borane. Similarly, bicyclic imidazolines have been prepared from triamines and thiocarbonyl diimidazole (Entry 10, Table 14.3). Dehydration of polystyrene-bound monoacyl ethylene-1,2-diamines yields 4,5-dihydroimidazoles (cyclic amidines, Entry 5, Table 13.18). Several groups have reported the synthesis of 2-aminoimidazol-4-ones from resin-bound amino acid derivatives (e.g., Entry 6, Table 15.11). Most of these compounds are, however, unstable, and slowly decompose if dissolved in DMSO (Jesper Lau, private communication). 

---