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Resolution of the Atropochiral Biminap Ligand and Applications in Asymmetric Catalysis
Author(s) -
Abdellah Ibrahim,
Debono Nathalie,
Canac Yves,
Vendier Laure,
Chauvin Remi
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900663
Subject(s) - chemistry , ligand (biochemistry) , palladium , tsuji–trost reaction , chiral ligand , enantiomeric excess , enantiomer , crystallization , dimethyl malonate , enantioselective synthesis , absolute configuration , catalysis , kinetic resolution , medicinal chemistry , chiral resolution , solvent , malonate , stereochemistry , organic chemistry , biochemistry , receptor
Abstract Enantiomeric resolution of the rac ‐biminap ligand is achieved through fractional crystallization of four diastereoisomeric palladium complexes involving ortho ‐metallated enantiomerically pure ( R )‐dimethyl(1‐naphthylethyl)amine as a chiral auxiliary. After decomplexation, the absolute configuration of ( R )‐biminap and ( S )‐biminap has been unambiguously attributed by single‐crystal X‐ray crystallography, and their stereochemical purity is confirmed by measurement of their optical rotation and by re‐derivatization with the initial resolving chiral complex. Palladium complexes of biminap are shown to efficiently catalyze Tsuji–Trost allylic substitution of 3‐acetoxy‐1,3‐diphenylpropene by sodium dimethyl malonate. In the asymmetric version using the enantiomerically pure ( R )‐biminap ligand, significant solvent and anion effects are evident, and an ee up to 90 % is obtained.