The ready accessibility of (R)- α -aminoadipic acid by enzymatic cleavage of cephalosporin C (CephC) in the production of 7-aminocephalosporanic acid (7-ACA) on a large scale makes it a favorable chiral pool building block for the synthesis of unusual amino acids. A route for the synthesis of C-5-alkenyl and C-6-alkylidene derivatives of (R)-pipecolic acid is described which utilizes (R)- α -aminoadipic acid as the enantiomerically pure starting material. Moreover, the synthesis of azido and triazolyl derivatives of (R)- α -aminoadipic acid is reported.