Abstract: | Starting with achiral phosphines and (1S,2S)‐2‐(methylamino)‐1‐phenylpropan‐1‐ol ((+)‐pseudoephedrine) or (1R,2S)‐2‐(methylamino)‐1‐phenylpropan‐1‐ol ((−)‐ephedrine), as chiral auxiliaries, diastereoisomerically pure oxazaphospholes were prepared (Scheme 1). The configuration at the P‐atom is controlled by the configuration at the Ph‐substituted C(1) of (+)‐pseudoephedrine or (−)‐ephedrine, respectively. This was confirmed by X‐ray crystal‐structure analyses of two intermediate compounds in the synthesis route to the chiral triarylborane‐phosphane adducts. |