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Bulky P* ‐Chirogenic Diazaphospholidines as Monodentate Ligands for Asymmetric Catalysis
Author(s) -
Gavrilov Konstantin N.,
Benetskiy Eduard B.,
Grishina Tatiana B.,
Rastorguev Eugenie A.,
Maksimova Marina G.,
Zheglov Sergey V.,
Davankov Vadim A.,
Schäffner Benjamin,
Börner Armin,
Rosset Stephane,
Bailat Gaelle,
Alexakis Alexandre
Publication year - 2009
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.200900058
Subject(s) - chemistry , diethylzinc , octane , denticity , allylic rearrangement , catalysis , enantioselective synthesis , medicinal chemistry , conjugate , stereochemistry , organic chemistry , crystal structure , mathematical analysis , mathematics
Abstract A series of easily prepared bulky P *‐chiral diamidophosphites based on (2 R ,5 S )‐3‐phenyl‐1,3‐diaza‐2‐phosphabicyclo[3.3.0]octane and (2 R ,5 S )‐3‐( p ‐bromophenyl)‐1,3‐diaza‐2‐phosphabicyclo[3.3.0]octane backbones have been designed and developed. Ligands of this type exhibited high enantioselectivities in Pd‐catalysed allylic substitution reactions of ( E )‐1,3‐diphenylallyl acetate with NaSO 2 p Tol (up to 87 % ee ), CH 2 (CO 2 Me) 2 (up to 92 % ee ), (C 3 H 7 ) 2 NH (up to 93 % ee ) and (CH 2 ) 4 NH (up to 99 % ee ). These novel stereoselectors have also been successfully employed in Rh‐catalysed asymmetric hydrogenations of dimethyl itaconate (up to 76 % ee ), methyl ( Z )‐2‐acetamido‐3‐phenylacrylate (up to 73 % ee ) and methyl 2‐acetamidoacrylate (up to 98 % ee ). Cu‐catalysed conjugate addition of diethylzinc to cyclohexenone leads to a maximum of 70 % ee with quantitative conversion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)