Polymer Supports in Synthesis

Akelah, Heterogeneous Organic Synthesis using Functionalised Polymers , Synthesis, 1981, 413. 

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Guyot, A. (1988) Synthesis and Structure of Polymer Supports, in Synthesis and Separations Using Functional Polymers (eds D.C. Sherrington and P. Hodge), John Wiley Sons, Inc., New York, pp. 1-42. 

Guyot, A. Synthesis and structure of polymer supports. In Synthesis and Separations using Functional Polymers, Sherrington, D.C., Hodge, P., Eds. John Wiley and Sons London 1988, 1-42. 

A. Guyot, Synthesis and stmcture of polymer supports , in Synthesis and Separations Using Functional Polymers , DC. Sherrington, R. Hodge, eds., John Wiley and Sons, Chichester, UK, Chap 1, p 1, 1988... 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

When the polymer was prepared by the suspension polymerization technique, the product was crosslinked beads of unusually uniform size (see Fig. 16 for SEM picture of the beads) with hydrophobic surface characteristics. This shows that cardanyl acrylate/methacry-late can be used as comonomers-cum-cross-linking agents in vinyl polymerizations. This further gives rise to more opportunities to prepare polymer supports for synthesis particularly for experiments in solid-state peptide synthesis. Polymer supports based on activated acrylates have recently been reported to be useful in supported organic reactions, metal ion separation, etc. [198,199]. Copolymers are expected to give better performance and, hence, coplymers of CA and CM A with methyl methacrylate (MMA), styrene (St), and acrylonitrile (AN) were prepared and characterized [196,197]. 

Murakami, Y. Functionaiited Cyclophanes as Catalysts and Enzyme Models. 115, 103-151 (1983). Mutter, M., and Pillai, V. N. R. New Perspectives in Polymer-Supported Peptide Synthesis. 106, 119-175 (1982). 

Leznoff CC, Wong JY. The use of polymer supports in organic synthesis. III. Selective chemical reactions on one aldehyde group of symmetrical aldehydes. Can J Chem 1973, 51 3756-3764. 

Since better selectivity was obtained when the ligands were removed from the dihydropyran-derivatized polymer support, after synthesis they were cleaved from the polymer and used in catalysis without purification. Comparable selectivities were obtained with ligands that were used directly without purification and selected examples where the ligands were purified prior to use. For such an approach to be useful in catalyst development, it is critical that the material from the synthesis be of sufficient purity to be used without purification. 

A drastically distinct use of a polymer support in oligosaccharide synthesis was devised in connection with p-methoxybenzyl (PMB)-assisted intramolecular... 

E. Garcia-Junceda, et al. Biocatalysis and Biotransformation 2000, 38, 271-281. MPEG consists of a polyethylene glycol 5000 monomethyl ester, see J.J. Kre-pinsky. Advances in polymer-supported solution synthesis of oligosaccharides, In Modern Methods in Carbohydrate Synthesis... 

Sauvagnat, B., Lamaty, F., Lazaro, R. and Martinez, J., Poly(ethylene glycol) as solvent and polymer support in the microwave assisted parallel synthesis of aminoacid derivatives, Tetrahedron Lett., 2000, 41, 6371. 

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