Reagents polymer-supported, degree

A nonpolar solvent favors conformation A, whereas conformation B is favored by more polar solvents (e.g. dimethylformamide, hexamethylphosphoric triamide) because the cation is more solvated (cf. Table 9, entries 1 and 2). However, this solvent effect is absent when BujP Cu" is used as counterion. Conformation A is more favored by relatively small counterions, such as the lithium and sodium ion, as compared to the larger potassium ion, due to the higher degree of association of the former. Steric strain between ASG and ASG is minimized in conformation B. Conformations A and B lead to trans- and c -substituted cyclopropanes, respectively. A study of cyclopropane esters, -in which the stereoselectivity of the reaction of polymer-supported reagents was compared with molecules of low-molecular weight, made clear that the steric and polar microenvironment of the polymer-supported reaction is not different enough in bulk to influence the selectivity substantially. Nevertheless, a specific influence of the solid phase can be observed at low temperatures. 

The use of insoluble polymeric carriers has greatly simplified the synthesis of peptides purification of the growing peptide chain in the repetitive steps is achieved by filtration procedures that simply remove all soluble reagents and byproducts from the reaction medium, whilst the covalently resin-hnked macromolecule is retained on the insoluble polymeric support. In all sohd-phase reactions of this type, the polymeric support represents the medium on or in which the chemical reaction takes place. Correspondingly, this medium is represented by the total amount of insoluble polymer present, which in the case of polymeric beads is divided into small, individual reaction compartments. Resin parameters such as the degree of crosshnking, the polarity of the resin, its sweUing properties, mass-transport, phase transitions, bead size, and the particle size distribution therefore have to be taken into serious consideration. 

---