Enantioselective Michael addition of malonates to α,β-unsaturated ketones catalyzed by rare-earth metal amides RE[N(SiMe3)2]3 with phenoxy-functionalized amino alcohol proligands.

[Display omitted] • The enantioselective Michael addition of malonates with unsaturated ketones. • Catalyzed by samarium amide Sm[N(SiMe 3) 2 ] 3 together with the chiral phenoxy-functionalized amino alcohol proligands. • The products with good group tolerance, mostly in high to excellent yields (85–98%) and good to excellent ee values (50– >99%). • A possible mechanism was proposed. A combination of rare-earth metal amides RE[ N (SiMe 3) 2 ] 3 and chiral phenoxy-functionalized amino alcohol proligands was developed to realize the enantioselective Michael addition of malonates with unsaturated ketones. The reactions catalyzed by samarium amide Sm[ N (SiMe 3) 2 ] 3 were performed best together with the chiral proligand H 3 L1 (H 3 L1 = 2,4-di- tert -butyl-6-((((1 S ,2 R)-2-hydroxy-1,2-diphenylethyl) amino)methyl)phenol) in DCE with good group tolerance, mostly in high to excellent yields (85–98 %) and good to excellent ee values (50− >99 %). The possible mechanism was also proposed. [ABSTRACT FROM AUTHOR]