Abstract
Some chiral sodium alkoxides can be used as catalysts in the asymmetric Michael reaction as exemplified by the 1,4-addition of an achiral NiII complex of the Schiff base derived from glycine andN-(2-pyridylcarbonyl)-o-aminobenzophenone (1) to methyl methacrylate (2) or methyl acrylate (14). The products of the reaction of1 with2,viz., the corresponding diastereomeric complexes of 4-methylglutamic acid, are formed in dissimilar amounts (de 26–85%); theee value for the major diastereomer (2S,4R)-3a is 28%. After recrystallization, the enantiomeric purity of complex3a increases toee>85%. Acidcatalyzed hydrolysis of the enantiomerically enriched complex3a affords (2S,4R)-4-methylglutamic acid (ee>85%). The complex of glutamic acid15 resulting from the reaction of1 with14 is formed with anee of 45%. After recrystallization, the enantiomeric purities of complex15 and glutamic acid increase toee>90%.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 76–83, January, 1998.
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Belokon', Y.N., Kochetkov, K.A., Churkina, T.D. et al. The first example of asymmetric Michael reaction catalyzed by chiral alkali metal alkoxides. Russ Chem Bull 47, 74–81 (1998). https://doi.org/10.1007/BF02495512
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DOI: https://doi.org/10.1007/BF02495512