P*,N-Bidentate Amino Phosphoramidites: New Highly Effective Ligands for Pd-Catalysed Asymmetric Allylic Substitution

✍ Scribed by Konstantin N. Gavrilov; Vasily N. Tsarev; Alexei A. Shiryaev; Oleg G. Bondarev; Sergey E. Lyubimov; Eduard B. Benetsky; Alexander A. Korlyukov; Mikhail Yu. Antipin; Vadim A. Davankov; Hans-Joachim Gais

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 135 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200300270

✦ Synopsis

Abstract

New chiral P*,N‐hybrid amino phosphoramidites have been obtained by one‐step phosphorylation of amino alcohols. Complexation of the new ligands with [Rh(CO)~2~Cl]~2~ and [Pd(allyl)Cl]~2~ gave the corresponding chelate complexes [Rh(CO)Cl(η^2^‐P,N)] and [Pd(allyl)(η^2^‐P,N)]^+^BF~4~^−^, which subsequently afforded up to 90% ee in the asymmetric Pd‐catalysed sulfonylation of 1,3‐diphenyl‐2‐propenyl acetate with sodium p‐toluenesulfinate. In the enantioselective alkylation of 1,3‐diphenyl‐2‐propenyl acetate with dimethyl malonate, up to 98% enantioselectivity was achieved with [Pd(allyl)(η^2^‐P,N)]^+^BF~4~^−^ complexes as chiral catalysts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)