Preparation of Fluoroalkyl Imines, Amines, Enamines, Ketones, α-Amino Carbonyls, and α-Amino Acids from Primary Enamine Phosphonates†
journal contributionposted on 10.12.2004, 00:00 by Francisco Palacios, Ana María Ochoa de Retana, Sergio Pascual, Julen Oyarzabal
A simple method for preparation of fluoroalkyl β-enaminophosphonates 1 from alkylphosphonates 2 and perfluoroalkyl nitriles 3 is reported. Olefination reaction of functionalized phosphates 1 with aldehydes gives α,β-unsaturated imines 5. Acid hydrolysis of these fluoroalkyl derivatives 5 affords α,β-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 α-amino aldehydes 12, α-amino ketones 13, or α-amino acid derivatives 14.