The use of chemoselective ligation methods and orthogonal protection techniques allows access to Template-Assembled Synthetic Protein (TASP) mols. exhibiting a large variety of packing topologies. This is demonstrated for the synthesis of an antiparallel 4a-helical bundle TASP by condensing amphiphilic peptide blocks, contg. aldehyde functions at the C- or N-terminus, to a selectively addressable topol. template via oxime bond formation. The resulting antiparallel 4a-helix TASP is obtained in high yield and shows a template-induced helical conformation. [on SciFinder (R)]