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P ‐Chiral Monodentate Diamidophosphites − New and Efficient Ligands for Palladium‐Catalysed Asymmetric Allylic Substitution
Author(s) -
Tsarev Vasily N.,
Lyubimov Sergey E.,
Shiryaev Alexei A.,
Zheglov Sergey V.,
Bondarev Oleg G.,
Davankov Vadim A.,
Kabro Anzhelika A.,
Moiseev Sergey K.,
Kalinin Valery N.,
Gavrilov Konstantin N.
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300694
Subject(s) - chemistry , allylic rearrangement , denticity , palladium , cationic polymerization , medicinal chemistry , steric effects , substitution reaction , enantioselective synthesis , stereochemistry , catalysis , organic chemistry , crystal structure
Novel P *‐monodentate diamidophosphite ligands have been prepared by a one‐step phosphorylation of alcohols or amines. Both the electronic and the steric demands of the ligands have been estimated quantitatively. Neutral [Pd(allyl)Cl(L)] and cationic [Pd(allyl)(L) 2 ] + BF 4 − complexes have been obtained by starting from [Pd(allyl)Cl] 2 . The new ligands have demonstrated high enantioselectivity in the Pd‐catalysed allylic substitution reactions of 1,3‐diphenylallyl acetate with NaSO 2 p Tol (up to 97% ee ), PhCH 2 NH 2 (up to 95% ee ) and CH 2 (CO 2 Me) 2 (up to 97% ee ). Application of the P *‐monodentate diamidophosphites to the asymmetric catalytic synthesis of chiral carborane derivatives has also been demonstrated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)