886576-75-6Relevant articles and documents
Acylative kinetic resolution of racemic methyl-substituted cyclic alkylamines with 2,5-dioxopyrrolidin-1-yl (: R)-2-phenoxypropanoate
Bartashevich, Ekaterina V.,Chulakov, Evgeny N.,Ezhikova, Marina A.,Gruzdev, Dmitry A.,Kodess, Mikhail I.,Korolyova, Marina A.,Krasnov, Victor P.,Levit, Galina L.,Tumashov, Andrey A.,Vakarov, Sergey A.
supporting information, p. 862 - 869 (2022/02/03)
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.
Asymmetric intramolecular hydroamination of alkenes in mild and wet conditions - Structure and reactivity of cationic binuclear gold(I) catalysts
Abadie, Marc-Antoine,Trivelli, Xavier,Medina, Florian,Capet, Frederic,Roussel, Pascal,Agbossou-Niedercorn, Francine,Michon, Christophe
, p. 2235 - 2239 (2014/08/18)
A selected diphosphine binuclear gold(I) chloride complex was combined with a silver salt to catalyze efficiently, for the first time, the asymmetric intramolecular hydroamination of alkenes with high conversions and enantioselectivities, in mild conditions and in presence of water. Both enantiomers of the products could be obtained by controlling the molecular ion-pairs through the solvent polarity. The gold(I) cationic active species was characterized unambiguously at the solid state by X-ray analysis and in solution by DOSY 1H NMR experiments. No contribution of silver chloride was observed on the bonding mode of the catalyst.
Room temperature palladium-catalyzed intramolecular hydroamination of unactivated alkenes
Michael, Forrest E.,Cochran, Brian M.
, p. 4246 - 4247 (2007/10/03)
A mild and facile Pd-catalyzed intramolecular hydroamination of unactivated alkenes is described. This reaction takes place at room temperature and is tolerant of synthetically useful acid-sensitive functional groups. The formation of hydroamination products rather than oxidative amination products is due to the use of a tridentate ligand on Pd which effectively inhibits β-hydride elimination. Copyright