A new series of P*-chiral diamidophosphites with 1,3,2-diazaphospholidine rings, based on (S a )-or (R a )-BINOL and their easily accessible derivatives, has been synthesized for the first time and tested in asymmetric transition metal catalysis. Up to 99% ee was achieved in the rhodium-catalyzed asymmetric hydrogenation of functionalized olefins and in the palladium-catalyzed allylic substitution. The influence of the nature of the donor atoms and denticity on the asymmetric induction is discussed. In addition, the first example of a successful platinum-catalyzed asymmetric allylic amination (up to 86% ee) with participation of organophosphorus ligands is considered.

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Monodentate phosphite and diamidophosphite ligands have been developed based on Omethyl-BINOL. These chiral ligands are easy to prepare from readily accessible phosphorylating re-The new ligands have demonstrated excellent enantioselectivity in the palladium-catalysed allylic substitution reactions of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate (up to 99 % ee), pyrrolidine (up to 97 % ee), dipropylamine (up to 95 % ee) and dimethyl malonate (up to 99 % ee). In the palladium-catalysed deracemization of ethyl (E)-1,3-diphenylallyl carbonate, up to 96 % enantioselectivity has been achieved. The diamidophosphite ligands have exhibited very good enantioselectivity in the Rh-catalysed asymmetric hydrogenation of dimethyl itaconate (up to 90 % ee).

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– = BF4–, Cl–, I–, CH12B11–) – were obtained and all new compounds were fully characterized by 1H, 13C, 31P 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 & Co. KGaA, 69451 Weinheim, Germany, 2005)

Synthesis of diastereomeric mono and bidentate diamidophosphites bearing P* stereo centers and phosphabicyclo[3.3.0]octane backbone and their coordination with rhodium(I) and palladium(II) are considered. Their use in Rh catalyzed asymmetric allylation allowed one to achieve 87% ee values and the use in Rh catalyzed asymmetric hydrogenation gave up to 98% ee.Asymmetric metallocomplex catalysis represents a highly efficient methodology for the preparation of valu able enantiomerically pure organic and organoelement compounds. 1-3 Chemical and optical yields close to quan titative are achieved in enantioselective catalytic transfor mations due to the most careful optimization of various reaction parameters. The key unit of the optimization process is the correct choice of the ligand group and ratio nal design of each ligand from this ligand group. 4 Among phosphorus containing ligands, the predominant position is occupied by P,P bidentate ligands. However, in the recent time many researchers use more electron with drawing compounds of the phosphite type. The latter are especially attractive by simplicity of their preparation from accessible precursors and stability to oxidative destruc tion. In addition, they are characterized by the pronounced π acidity and low cost. 5-10 At the same time, only several promising P*,P* bidentate ligands of the phosphite type bearing stereogenic phosphorus atoms are described. 11-13 This is rather surprising, because it is well known 2 that ligands with asymmetric donor atoms are excellent stereoselectors.It is worth noting that cheap chiral diols bearing several C* stereocenters are a very abundant pool for the synthesis of P,P bidentate phosphites. 4-10 In particular, a series of phosphite and phosphinite ligands 1-3 based on 1,4:3,6 dianhydro D mannitol (see below) were success fully used in selected reactions of asymmetric hydrogena tion and allylic substitution. 14-17 R = R´ = H (a); R = Me, R´ = H (b); R = R´ = Bu t (c)