AbstractCondensation of (±)‐1‐benzyl‐3‐methyl‐4‐piperidone (1) with aniline followed by trapping of the intermediate imine with cyanide generated a mixture of isomeric nitriles2Aand2B, the structures of which were established unambiguously by obtaining an X‐ray crystal structure on nitrile2B. Subsequent elaboration of the nitrile intermediates provided analogs of (±)‐cis‐N‐[1‐(2‐hydroxy‐2‐phenylethyl)‐3‐methyl‐4‐piperidyl]‐N‐phenylpropanamide having a second substituent (carbomethoxyl, carboethoxyl, methoxymethyl) at the piper‐idine 4‐position. The conversion of the carboxamide intermediates3Aand3Bto the carboalkoxyl intermediates5A, 5Band6Awas accomplished utilizing a modified esterification procedure. Proton nmr data are presented for both the final