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)2Cl]2, [Rh(COD)(THF)2]BF4, [Pd(allyl)Cl]2, [Pt(allyl)Cl]4, [Pd(COD)Cl2] and [Pt(COD)Cl2] was found to give chelate complexes [Rh(CO)(η2-P,N)Cl], [Rh(COD)(η2-P,N)]BF4, [M(allyl)(η2-P,N)]BF4 (M = Pd, Pt) and cis-[M(η2-P,N)Cl2] (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.

Graphical abstractNew chiral P,N-bidentate ferrocene- and cymantrene-based iminoarylphosphites were synthesised and their complexation with the Rh(I), Pd(II) and Pt(II) atoms investigated. The new ligands gave up to 97% ee in the enantioselective Pd-catalysed allylic alkylation and up to 96% ee in the Pd-catalysed allylic amination of 1,3-diphenyl-2-propenyl acetate.Figure optionsDownload full-size imageDownload as PowerPoint slide