Novel synthesis of alpha-trifluoromethylated alpha-amino acid derivatives from gamma-hydroxy-alpha-fluoro-alpha-trifluoromethyl carboxamides.
On treatment with an organoaluminum reagent such as trimethylaluminum or DIBAL-H, gamma-hydroxy-alpha-fluoro-alpha-trifluoromethyl carboxamides (1) give a single diastereomer of alpha-amino-alpha-trifluoromethyl-gamma-lactones (2), which are a ring-closed form of gamma-hydroxy-alpha-trifluoromethyl-alpha-amino acids. This intriguing reaction results from intramolecular replacement of the fluorine atom on the alpha-carbon atom with the nitrogen atom of the amide group, which occurs in an SN2 manner. [reaction: see text]
Ogu
Kenichi
K
Department of Applied Chemistry and Biotechnology, Faculty of Engineering, Chiba University, 1-33 Yayoicho, Inageku, Chiba 263-8522, Japan.
Matsumoto
Shoji
S
Akazome
Motohiro
M
Ogura
Katsuyuki
K
D000478:Alkylation; D000535:Aluminum; D000596:Amino Acids / Q000138:chemical synthesis*; D006900:Hydroxylation; D009682:Magnetic Resonance Spectroscopy; D008745:Methylation; D008958:Models, Molecular; D009942:Organometallic Compounds
D000596:Amino Acids; D009942:Organometallic Compounds; C444501:dimethylaluminum chloride; D000535:Aluminum