NH-Поліфлуороалкілімінофосфонати в синтезі оптично активних α-аміно-α-поліфлуороалкіл-γ-оксобутилфосфонових кислот

• Дата: 2019
• Автори: Stanko, O. V., Yelenich, Y. P., Onys’ko, P. P., Rassukana, Yu. V.
• Формат: Стаття
• Мова: Ukrainian
• Опубліковано: National University of Pharmacy 2019
• Теми: оptically active a-aminophosphonates; рolyfluoroalkylated aminophosphonic acids; іminophosphonates; stereoselective synthesis; UDC 547.241 47.398 542.91; оптически активные a-аминофосфонаты; полифторалкиламинофосфоновые кислоты; иминофосфонаты; стереоселективный синтез; УДК 547.241 547.398 542.91; оптично активні α-амінофосфонати; поліфлуороалкіламінофосфонові кислоти; імінофосфонати; стереоселективний синтез; УДК 547.241 547.398 542.91
• Онлайн доступ: https://ophcj.nuph.edu.ua/article/view/ophcj.19.967
• Назва журналу: Journal of Organic and Pharmaceutical Chemistry

Aim. To develop the preparative method for the synthesis of optically active α-amino-α-polyfluoroalkyl-γ-oxobutylphosphonic acids as new promising chiral building blocks.Results and discussion. It has been shown that the reaction of NH-polyfluoroalkyl aminophosphonates with acetone in the presence of a catalytic amount of L- or D-proline occurs stereoselectively to give enantiomerically enriched (R)- or (S)-α-amino-γ-oxophosphonates, respectively. The resulting optically active phosphonates were converted into water-soluble α-amino-γ-oxophosphonic acids isolated in the individual form as hydrochlorides.Experimental part. By the reaction of рolyfluoroacetonitriles with diethyl phosphite in the presence of triethylamine the series of NH-рolyfluoroalkyl іminophosphonates were synthesized. They undergo the prolinecatalysed reaction with acetone to form optically active α-amino-α-polyfluoroalkyl-γ-oxobutyl phosphonates. The latter were converted into the corresponding phosphonic acids by the reaction with hydrogen chloride. The structures of the compounds synthesized were confirmed by analytical and spectral NMR (1Н, 13С, 19F, 31Р) methods.Conclusions. Based on the proline-catalyzed reaction of NH-рolyfluoroalkyl іminophosphonates with acetone the preparativesynthesis method for new chiral building blocks – α-amino-α-polyfluoroalkyl-γ-oxobuthylphosphonates and phosphonic acids has been developed.