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P* , N ‐Bidentate Amino Phosphoramidites: New Highly Effective Ligands for Pd‐Catalysed Asymmetric Allylic Substitution
Author(s) -
Gavrilov Konstantin N.,
Tsarev Vasily N.,
Shiryaev Alexei A.,
Bondarev Oleg G.,
Lyubimov Sergey E.,
Benetsky Eduard B.,
Korlyukov Alexander A.,
Antipin Mikhail Yu.,
Davankov Vadim A.,
Gais HansJoachim
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300270
Subject(s) - chemistry , enantioselective synthesis , tsuji–trost reaction , medicinal chemistry , denticity , allylic rearrangement , propenyl , chelation , dimethyl malonate , catalysis , stereochemistry , organic chemistry , crystal structure
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)