Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher e...

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Bibliographic Details
Published in:Tetrahedron 2013-11, Vol.69 (47), p.10003-10008
Main Authors: Yoshida, Masanori, Nagasawa, Yuki, Kubara, Ami, Hara, Shoji, Yamanaka, Masahiro
Format: Article
Language:English
Subjects:
Amino acids
Asymmetric synthesis
Asymmetry
Catalysts
Cations
DFT calculation
Lithium
Mathematical analysis
Michael addition
Michael reaction
Organocatalysis
Origins
Primary amino acid
Tetrahedrons
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Summary:A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2013.09.066