γ4-Tripeptides and γ4-hexapeptides, 1 – 4, with OH groups in the 2- or 3-position on each residue have been prepared. The corresponding 2-hydroxy amino acids were obtained by Si-nitronate (3+2) cycloadditions to the acryloyl derivative of Oppolzer's sultam and Raney-Ni reduction of the resulting 1,2-oxazolidines (Scheme 1). The 3-hydroxy amino acid derivatives were prepared by chain elongation via Claisen condensation of Boc-Ala-OH, Boc-Val-OH, and Boc-Leu-OH, and NaBH4 reduction of the methyl 4-amino 3-oxo carboxylates formed (Scheme 2). The N-Boc hydroxy amino acids were coupled in solution to give the γ-peptides. CD Spectra of the new types of γ-peptides were recorded and compared with those of simple γ2-, γ3-, γ4-, and γ2,3,4-peptides (Figs. 3, 4, and 5). An intense Cotton effect at ca. 200 nm ([Θ]=−2⋅105 deg⋅cm2⋅dmol−1) indicates that the hexapeptide built of (3R,4S)-4-amino-3-hydroxy acids (with the side chains of Val, Ala, Leu) folds to a secondary structure so far unknown. The stability of peptides from β- and γ-amino acids, which carry heteroatoms on their backbones is discussed (Fig. 1). Positions on the γ-peptidic 2.614 helix are identified at which non-H-atoms are `allowed' (Fig. 2).