About diastereoselective oxidations of ferrocenyl amino alcohols

• Published in: Tetrahedron 2004-02, Vol.60 (7), p.1549-1556
• Main Authors: Delacroix, Olivier, Andriamihaja, Bakolinirina, Picart-Goetgheluck, Sophie, Brocard, Jacques
• Format: Article
• Language: English
• Subjects: Alcohol; Diastereoselectivity; Ferrocene; Oxidation
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2003.12.004

Oxidation of some 2-( N, N-dimethylaminomethyl)ferrocenylalkylcarbinols by MnO 2 is totally diastereoselective: only one diastereomer is oxidized. A study was performed to highlight the influential factors of this phenomenon. Several ferrocenyl alcohols have been studied. First, two diastereomers of the ferrocenyl amino alcohol bearing a deuterium as an R group have been synthesized and oxidized. The good reactivity of both diastereomers displayed the importance of the size of the alkyl group, which needs to be bulkier than a deuterium. The synthesis and the oxidation of endo- and exo-α-hydroxy [4](1,2)ferrocenophane enabled the elimination of the hypothesis involving the spatial position of the hydroxy group, while the two diastereomers were oxidized. The replacement of the dimethylamino group by a methoxy or a methyl, the oxidation of these compounds, and the study of the preferential conformation of each diastereomer showed clearly the influence of an intramolecular hydrogen bond. So,the diastereoselectivity was shown to depend on the steric bulk of the alkyl group and on the presence of a strong intramolecular hydrogen bond between the hydroxy group and the nitrogen. Graphic