Enantioselective Metalation of N,N‐Diisopropylferrocenecarboxamide and Methyl Ferrocenecarboxylate Using Lithium‐Metal Chiral Bases
Identifieur interne : 001280 ( Main/Exploration ); précédent : 001279; suivant : 001281Enantioselective Metalation of N,N‐Diisopropylferrocenecarboxamide and Methyl Ferrocenecarboxylate Using Lithium‐Metal Chiral Bases
Auteurs : Gandrath Dayaker ; David Tilly ; Floris Chevallier ; Göran Hilmersson [Suède] ; Philippe C. Gros [France] ; Florence Mongin [France]Source :
- European Journal of Organic Chemistry [ 1434-193X ] ; 2012-10.
Descripteurs français
- Wicri :
- topic : Zinc.
English descriptors
- KwdEn :
Abstract
Enantioselective deprotonative metalations of substituted ferrocenes using mixed lithium‐metal bases are described. Using N,N‐diisopropylferrocenecarboxamide as substrate, magnesium, iron, cobalt, zinc, and cadmium were tested as metals in bis[(S)‐1‐phenylethyl]amido‐based combinations; after interception of the metalated species with iodine, very high enantiomeric excess (96 %) but low yield was obtained with cobalt, whereas zinc and cadmium only gave 27 and 30 % ee, respectively, but in excellent yields. The small alkyl groups methyl and ethyl were identified as particularly suitable in the reaction using the putative dialkyl bis[(S)‐1‐phenylethyl]amido‐based lithium and dilithium zincates. The dimethyl dilithium zincate was selected for a study of dependency on the temperature, reaction time, and amount of base. Increased enantioselectivities with temperature, reaction time, and amount of base were noted (ee = 86 % at 0 °C after 2 h, 2 equiv. of base). The best result using methyl ferrocenecarboxylate as substrate was observed without alkyl ligand.
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DOI: 10.1002/ejoc.201200965
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