Enantioselective fluorination of organic molecules. I. Synthetic studies of the agents for electrophilic, enantioselective fluorination of carbanions.
In order to develop novel methods for electrophilic and enantioselective fluorination of active methine compounds, preliminary experiments were carried out. The N-tosyl derivative 5 obtained from D-phenylglycine was fluorinated with FClO3 or diluted F2 gas to give the N-fluoro-N-tosyl derivative 6. N-tosyl- or N-mesyl-(S)-alpha-phenethylamine 7 or 8 was subjected to FClO3 fluorination to produce the corresponding N-fluoro derivative, 10 or 11, respectively. Enantioselective fluorination of some methine compounds was attempted employing the above N-fluoro agents. Best result was obtained when 2-benzyl-1-tetralone/KHMDS was treated with 10 to produce the fluorinated tetralone 17 in 53% yield with enantiomeric excess (ee) of 48%.
Takeuchi
Y
Y
Faculty of Pharmaceutical Sciences, Toyama Medical & Pharmaceutical University, Japan.
Satoh
A
A
Suzuki
T
T
Kameda
A
A
Dohrin
M
M
Satoh
T
T
Koizumi
T
T
Kirk
K L
KL
D000838:Anions / Q000378:metabolism*; D002244:Carbon / Q000378:metabolism; D002851:Chromatography, High Pressure Liquid; D005459:Fluorides / Q000737:chemistry; D005461:Fluorine / Q000378:metabolism*; D005663:Furans; D005998:Glycine / Q000031:analogs & derivatives; D006860:Hydrogen Bonding; D007202:Indicators and Reagents / Q000138:chemical synthesis*; D008956:Models, Chemical; D010627:Phenethylamines / Q000737:chemistry / Q000378:metabolism; D013237:Stereoisomerism; D013464:Sulfuric Acids / Q000737:chemistry
D000838:Anions; D005663:Furans; D007202:Indicators and Reagents; D010627:Phenethylamines; D013464:Sulfuric Acids; D005461:Fluorine; C029261:phenethylamine; C018674:tetrahydrofuran; D002244:Carbon; C046106:fluorosulfonic acid; D005459:Fluorides; D005998:Glycine