The N‐silylated chiral amines TMS‐SAMP and TMS‐RAMP can be employed for stereoselective CN bond formation with enantiomeric excesses of 90‐80%. In these reactions, the corresponding hydrazinoesters are formed initially, which are subsequently cleaved hydrogenolytically to give the desired β‐amino acids 1. R = alkyl, R′ = Me, tBu. (Figure Presented.) Copyright © 1995 by VCH Verlagsgesellschaft mbH, Germany