Preparation of fluoroalkyl imines, amines, enamines, ketones, alpha-amino carbonyls, and alpha-amino acids from primary enamine phosphonates.
A simple method for preparation of fluoroalkyl beta-enaminophosphonates 1 from alkylphosphonates 2 and perfluoroalkyl nitriles 3 is reported. Olefination reaction of functionalized phosphates 1 with aldehydes gives alpha,beta-unsaturated imines 5. Acid hydrolysis of these fluoroalkyl derivatives 5 affords alpha,beta-unsaturated ketones 6, while their selective reduction with hydrides leads to the formation of allylamines 7, enamines 8, and saturated ketones 9 or amines 10. Selective oxidative cleavage of the carbon-carbon double bond of allylamines 7 gives fluorinated alpha-amino aldehydes 12, alpha-amino ketones 13, or alpha-amino acid derivatives 14.
Palacios
Francisco
F
Departamento de Química Orgánica I, Facultad de Farmacia, Universidad del País Vasco, Apartado 450, 01080 Vitoria, Spain. qoppagaf@vc.ehu.es
Ochoa de Retana
Ana María
AM
Pascual
Sergio
S
Oyarzabal
Julen
J
D000079:Acetaldehyde / Q000138:chemical synthesis*; D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry; D000596:Amino Acids / Q000138:chemical synthesis*; D007097:Imines / Q000138:chemical synthesis*; D007659:Ketones / Q000138:chemical synthesis*; D015394:Molecular Structure; D063065:Organophosphonates / Q000737:chemistry*
D000588:Amines; D000596:Amino Acids; D007097:Imines; D007659:Ketones; D063065:Organophosphonates; D000079:Acetaldehyde