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Easily Accessible ChiralP,N-Bidentate Aryl Phosphites, Their Complexation and Application in Enantioselective Allylic Alkylation, Sulfonylation and Hydrosilylation

2002; Wiley; Volume: 2002; Issue: 6 Linguagem: Inglês

10.1002/1099-0682(200206)2002

1099-0682

Konstantin N. Gavrilov, Oleg G. Bondarev, R. V. Lebedev, Alexei A. Shiryaev, S. E. Lyubimov, Alexei I. Polosukhin, G.V. Grintselev-Knyazev, Konstantin А. Lyssenko, Sergey K. Moiseev, Nikolay S. Ikonnikov, V. N. Kalinin, Vladim A. Davankov, A.V. Korostylev, Hans‐Joachim Gais,

Synthetic Organic Chemistry Methods

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)