The first gem-disubstituted β 2,2-amino acid possessing only axial chirality, was synthesized by bis-alkylation of methyl or ethyl cyanoacetate with both racemic and enantiomerically pure ( R)-2,2′-bis-(bromomethyl)-1,1′-binaphthyl, followed by NaBH 4/CoCl 2 reduction of the cyano group, treatment of the resulting amino esters with Boc 2O and finally saponification of the ester function, to afford the C- and/or N-protected derivatives of 2′,1′:1,2;1′′,2′′:3,4-dinaphthcyclohepta-1,3-diene-6-aminomethyl-6-carboxylic acid: ( RS)- and ( R)-X-β 2,2-HBin-OR (X=Boc; H) (R=Me, Et or H). For the medium-scale resolution of β 2,2-HBin, the racemic amino esters ( RS)-H-β 2,2-HBin-OR (R=Me, Et) were treated with benzoic anhydride and the resulting derivatives ( RS)-Bz-β 2,2-HBin-OR were saponified. The obtained ( RS)-Bz-β 2,2-HBin-OH was coupled with l-phenylalanine cyclohexylamide by the EDC/HOBt method to afford the dipeptide diastereoisomers Bz-( R)-Bin- l-Phe-NH-C 6H 11 and Bz-( S)-Bin- l-Phe-NH-C 6H 11, which were separated by chromatography. Complete hydrolysis under acidic conditions, followed by esterification of the resulting free amino acid enantiomers, N-protection and saponification, led to the enantiomerically pure derivatives ( R)- and ( S)-X-β 2,2-HBin-OR (X=Boc; H) (R=Me, H).