Homogeneous palladium-catalyzed enantioselective hydrogenation of 5-methylenhydantoin for the synthesis of L-Valine

• Published in: Journal of organometallic chemistry Vol. 929; p. 121572
• Main Authors: Hayouni, Safa, Michon, Christophe, Morvan, Didier, Bellière-Baca, Virginie, Agbossou-Niedercorn, Francine
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 14.12.2020; Elsevier
• Subjects: Asymmetric hydrogenation; Catalysis; Chemical Sciences; Coordination chemistry; Homogeneous catalysis; Hydantoin; Inorganic chemistry; L-Valine; Organic chemistry; Other; Palladium; Phosphine; Asymmetric hydrogenation; Palladium; L-Valine; Phosphine; Homogeneous catalysis; Hydantoin
• ISSN: 0022-328X; 1872-8561; 0022-328X
• DOI: 10.1016/j.jorganchem.2020.121572

•The enantioselective hydrogenation of 5-methylenhydantoin can lead to L-Valine.•A palladium catalyst allowed the asymmetric hydrogenation of 5-methylenhydantoin.•Hydrolysis of the corresponding hydrogenated product afforded L-Valine.•A partial racemization was observed upon hydrolysis and recovery of L-Valine. In this article, we present the development of a synthetic methodology based on homogeneous catalysis for the preparation of enantioenriched L-Valine aminoacid. The enantioselective hydrogenation of 5-methylenhydantoin has been developed through broad screenings of chiral ligands, metal precursors and reaction conditions including scale-up experiments and recyclability studies. A palladium catalyzed asymmetric hydrogenation of 5-methylenhydantoin afforded the corresponding hydrogenated product in a 70% enantiomeric excess using a substrate/catalyst ratio of 500/1. A partial racemization was observed upon hydrolysis and recovery of L-Valine. [Display omitted]