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À propos de : Asymmetric Synthesis of Metallocenes through EnantioselectiveAddition of Organolithium Reagents to 6-(Dimethylamino)fulvene        

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  • Asymmetric Synthesis of Metallocenes through EnantioselectiveAddition of Organolithium Reagents to 6-(Dimethylamino)fulvene
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  • Enantioselective addition of aryllithiums 2a−d (Ar = Ph (a), 2-MeC6H4 (b), 2-MeOC6H4 (c),1-naphthyl (d)) to 6-(dimethylamino)fulvene (1) in the presence of (−)-sparteine in toluene at −78°C generated chiral cyclopentadienyllithiums (4) substituted with an N,N-dimethylamino(aryl)methyl group, where the enantioselectivities are 51, 91, 90, and 83% for 4a, 4b, 4c, and 4d,respectively. Treatment of the chiral cyclopentadienides 4 with FeCl2 or Fe(acac)2 gave ferrocenes,which contain an N,N-dimethylamino(aryl)methyl side chain on both of the cyclopentadienyl rings.The enantiomeric purity of the chiral ferrocenes 7 thus obtained is 99% ee or higher for thosecontaining a 2-MeC6H4 (7b) or a 2-MeOC6H4 (7c) group.
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