Palacios Francisco, Ochoa de Retana Ana María, Pascual Sergio, Oyarzabal Julen
Departamento de Química Orgánica I, Facultad de Farmacia, Universidad del País Vasco, Apartado 450, 01080 Vitoria, Spain.
J Org Chem. 2004 Dec 10;69(25):8767-74. doi: 10.1021/jo048682m.
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.
报道了一种由烷基膦酸酯2和全氟烷基腈3制备氟代烷基β-烯胺基膦酸酯1的简单方法。官能化磷酸盐1与醛的烯化反应生成α,β-不饱和亚胺5。这些氟代烷基衍生物5的酸水解得到α,β-不饱和酮6，而用氢化物对其进行选择性还原则导致烯丙胺7、烯胺8以及饱和酮9或胺10的形成。烯丙胺7的碳-碳双键的选择性氧化裂解得到氟化α-氨基醛12、α-氨基酮13或α-氨基酸衍生物14。
