Easily Accessible Chiral P,N‐Bidentate Aryl Phosphites, Their Complexation and Application in Enantioselective Allylic Alkylation, Sulfonylation and Hydrosilylation

New chiral P,N-hybrid aryl phosphites have been obtained by one-step phosphorylation of amino and imino alcohols. Complexation of the new ligands with [Rh(CO)2Cl]2, [Pd(COD)Cl2] and [Pd(allyl)Cl]2 was found to give chelate complexes [Rh(CO)Cl(η2-P∩N)], [PdCl2(η2-P∩N)] and [Pd(allyl)(η2-P∩N)]+Cl−, respectively. With these new P,N-ligands, up to 82% ee enantioselectivity was achieved in the Pd-catalysed alkylation of ethyl 3-penten-2-yl carbonate with dimethyl malonate, up to 80% ee in the Pd-catalysed sulfonylation of methyl 3-penten-2-yl carbonate with sodium p-toluenesulfinate, and up to 50% ee in the Rh-catalysed hydrosilylation of acetophenone with diphenylsilane. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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