Iminoarylphosphites with ferrocenylidene and cymantrenylidene fragments: Coordination properties and use in palladium-catalysed asymmetric allylic substitution

Complexation of the chiral P , N -bidentate ferrocene- and cymantrene-based iminoarylphosphites with [Rh(CO) 2 Cl] 2 , [Rh(COD)(THF) 2 ]BF 4 , [Pd(allyl)Cl] 2 , [Pt(allyl)Cl] 4 , [Pd(COD)Cl 2 ] and [Pt(COD)Cl 2 ] was found to give chelate complexes [Rh(CO)(η 2 -P,N)Cl], [Rh(COD)(η 2 -P,N)]BF 4 , [M(allyl)(η 2 -P,N)]BF 4 (M = Pd, Pt) and cis -[M(η 2 -P,N)Cl 2 ] (M = Pd, Pt), correspondingly. With the new P , N -ligands, up to 97% ee was achieved in the asymmetric Pd-catalysed alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. In the enantioselective amination of 1,3-diphenyl-2-propenyl acetate with sodium diformylamide, up to 96% enantioselectivity was achieved.