Resin-to-resin acyl- and aminoacyl-transfer reactions using oxime supports

We describe a convergent approach to solid-phase synthesis in which two fra gments of a molecule are synthesized on independent supports and then conde nsed in a key resin-to-resin transfer reaction. This approach has been util ized for the synthesis of amides and ureas by transferring acyl groups and aminoacyl groups from p-nitrophenyl(polystyrene)ketoxime resin to amino aci d-functionalized Wang resins. Oxime resin-derived esters of peptides underg o transacylation to a solution-phase nucleophilic activator which then tran sfers the peptide to another resin bearing a nucleophilic amine terminus, r esulting in amide bond formation. Likewise, oxime resin-derived carbamates, prepared from phosgenated p-nitrophenyl(polystyrene)ketoxime resin, underg o thermolytic isocyanate liberation in solution, which reacts with a second resin bearing a nucleophilic amino terminus resulting in urea bond formati on.