Вид документа : Статья из журнала Шифр издания : Автор(ы) : Gruzdev D.A., Vakarov S. A., Korolyova M. A., Tumashov A. A., Chulakov E.N., Ezhikova M. A., Kodess M. I., Levit G. L., Krasnov V. P., Bartashevich E. V. Заглавие : Acylative kinetic resolution of racemic methyl-substituted cyclic alkylamines with 2,5-dioxopyrrolidin-1-yl (R)-2-phenoxypropanoate Место публикации : Organic & biomolecular chemistry. - 2022. - Vol. 20, № 4. - С. 862-869 Предметные рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The diastereoselective acylation of a number of racemic methyl-substituted cyclic alkylamines with active esters of 2-phenoxypropanoic acid was studied in detail. The ester of (R)-2-phenoxypropanoic acid and N-hydroxysuccinimide was found to be the most selective agent. The highest stereoselectivity was observed in the kinetic resolution of racemic 2-methylpiperidine in toluene at −40 °C (selectivity factor s = 73) with the predominant formation of (R,R)-amide (93.7% de). To explain the observed stereoselectivity, DFT modelling of the transition states in the reactions of the title acylating agent with 2-methylpiperidine and 2-methylpyrrolidine was performed. The calculated values were in good agreement with experimental data. It has been demonstrated that the acylation proceeds via a concerted mechanism, in which the addition of an amine occurs simultaneously with the elimination of the hydroxysuccinimide fragment. The high stereoselectivity of the (R,R)-amide formation is largely ensured by the lower steric hindrances in the transition states as compared to the formation of (R,S)-amide. Доп.точки доступа: Gruzdev, D.A.; Vakarov, S. A.; Korolyova, M. A.; Tumashov, A. A.; Chulakov, E.N.; Ezhikova, M. A.; Kodess, M. I.; Кодесс Михаил Исаакович; Levit, G. L.; Левит Галина Львовна; Krasnov, V. P.; Bartashevich, E. V.