Modular Synthesis of Novel Chiral Phosphorous Triamides Based on (S)‐N‐(Pyrrolidin‐2‐ylmethyl)aniline and Their Application in Asymmetric Catalysis

A set of new P‐chiral phosphorous triamides (PTAs) based on the (S)‐N‐(pyrrolidin‐2‐ylmethyl)aniline backbone was prepared by modular synthetic procedures. The chirality at phosphorus can be controlled to a large extent by the synthetic route, and high diastereomeric purities were achieved for most of the reported ligands. This ligand family was evaluated in the copper‐catalysed Michael addition of diethylzinc to cyclohex‐2‐enone, and moderate enantioselectivities were achieved. In the asymmetric nickel‐catalysed hydrovinylation of styrene, good conversions and chemoselectivities, together with promising enantioselectivities of up to 60 %, were obtained with the new PTA ligands even at relatively high reaction temperatures.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)