We furthermore conjectured that amino acids with bulky side chains could be coupled to the secondary rim if we used β-amino acids, as these would space the bulky side chain an additional methylene group further from the secondary rim. We tested this for β-tyrosine, reacting β-Boc-tyrosine and 3-NH2-β-CD under the same conditions as used to make 6. This afforded 12 in 65 % yields, after Boc-deprotection. In contrast, the same reaction with the corresponding α-amino acid, tyrosine, proved unsuccessful, presumably because the bulky phenol group sterically hinders reaction with 3-NH2-β-CD. This result further supports the principle that non-hindered linear nucleophiles are necessary for successful addition directly onto the secondary face. The β-amino acids are appealing substituents because they allow varied side-chains to be positioned particularly close to bound guests.