406951-72-2Relevant academic research and scientific papers
Fluoroalkyl α,β-unsaturated imines. Valuable synthetic intermediates from primary fluorinated enamine phosphonates
Palacios, Francisco,Pascual, Sergio,Oyarzabal, Julen,Ochoa De Retana, Ana M.
, p. 769 - 772 (2002)
(equation presented) A simple method for the preparation of fluoroalkyl allylamines or α,β-unsaturated ketones by an olefination reaction of primary enamine phosphonates and aldehydes, followed by selective reduction with hydrides or hydrolysis, is reported. Fluorinated β-amino nitriles are also obtained by an olefination reaction of primary enamine phosphonates with aldehydes and subsequent addition of metalated acetonitrile.
Dehydrogenation of perfluoroalkyl ketones by using a recyclable oxoammonium salt
Hamlin, Trevor A.,Kelly, Christopher B.,Leadbeater, Nicholas E.
supporting information, p. 3658 - 3661 (2013/07/19)
A novel dehydrogenation reaction of perfluoroalkyl ketones by the oxoammonium salt 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (4-NHAc-TEMPO+BF4-, Bobbitt's salt, 1) is described. The reaction proceeds under mildly basic conditions and appears to be unique to perfluoroalkyl ketones. A proposed mechanism for this unusual transformation is given. The byproduct of the reaction, 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinyloxy (1a), can easily be recovered and used to regenerate the oxoammonium salt. The dehydrogenation of perfluoroalkyl ketones by using an oxoammonium salt is reported. The reaction proceeds under mildly basic conditions and affords α,β-unsaturated products in fair to excellent yields. The reaction likely proceeds through a two-step sequence. The spent oxidant can easily be recovered and used to regenerate the oxoammonium salt. Copyright
Preparation of fluoroalkyl imines, amines, enamines, ketones, α-amino carbonyls, and α-amino acids from primary enamine phosphonates
Palacios, Francisco,Ochoa De Retana, Ana Maria,Pascual, Sergio,Oyarzabal, Julen
, p. 8767 - 8774 (2007/10/03)
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.
