Novel Highly Efficient <i>P</i>‐Chiral Ferrocenylimino Diamidophosphite Ligands for Pd‐Catalysed Asymmetric Allylation

Abstract

Abstract Novel P *‐chiral P , N ‐bidentate ligands were synthesized by treatment of ferrocene‐based imino alcohols with chlorophosphites derived from ( S )‐2‐anilinomethylpyrrolidine or ( S )‐prolinol. Metal chelate complexes with the ligands – [Rh(CO)(PN)Cl] and [Pd(PN)(allyl)] + X – (X – = BF 4 – , Cl – , I – , CH 12 B 11 – ) – were obtained and all new compounds were fully characterized by 1 H, 13 C, 31 P NMR, IR, MS (EI, CI, FAB, ESI and plasma desorption techniques) and X‐ray analysis (imino alcohol 2d and complex 7 ). P *‐Chiral diamidophosphites gave up to 97 % ee in the Pd‐catalysed allylic substitution of 1,3‐diphenylallyl acetate with dimethyl malonate and para ‐toluenesulfinate. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2005)