A Facile and Stereocontrolled Synthesis of gamma-Substituted gamma-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor

[摘要]：Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to alpha-substituted methyl acrylate leads to diastereomeric gamma-substituted gamma-fluoroglutamate precursors The tertiary center bearing the amino acid function in its natural configuration is generated with a high level of stereocontrol in contrast to the quaternary carbon center Diastereomeric gamma-substituted gamma-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity The Michael addition diastereoselectivity was studied for the asymmetric conjugate addition of fluorinated chiral beta-enaminoester to methyl alpha-acetamidoacrylate by F-19 and H-1 NMR experiments as well as ab initio computations An interfering conjunction between hindrance of the electrophile and a destabilizing effect of the fluorine atom borne by the nucleophile is revealed

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