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Article Dans Une Revue Chemistry - An Asian Journal Année : 2010

Resolution of the Atropochiral Biminap Ligand and Applications in Asymmetric Catalysis

Ibrahim Abdellah
Yves Canac
Laure Vendier
Rémi Chauvin

Résumé

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.

Dates et versions

hal-02907424 , version 1 (27-07-2020)

Identifiants

Citer

Ibrahim Abdellah, Nathalie Debono, Yves Canac, Laure Vendier, Rémi Chauvin. Resolution of the Atropochiral Biminap Ligand and Applications in Asymmetric Catalysis. Chemistry - An Asian Journal, 2010, 5 (5), pp.1225-1231. ⟨10.1002/asia.200900663⟩. ⟨hal-02907424⟩
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