title: The cinchona primary amine-catalyzed asymmetric epoxidation and hydroperoxidation of α,β-unsaturated carbonyl compounds with hydrogen peroxide.
abstract: Using cinchona alkaloid-derived primary amines as catalysts and aqueous hydrogen peroxide as the oxidant, we have developed highly enantioselective Weitz-Scheffer-type epoxidation and hydroperoxidation reactions of α,β-unsaturated carbonyl compounds (up to 99.5:0.5 er). In this article, we present our full studies on this family of reactions, employing acyclic enones, 5-15-membered cyclic enones, and α-branched enals as substrates. In addition to an expanded scope, synthetic applications of the products are presented. We also report detailed mechanistic investigations of the catalytic intermediates, structure-activity relationships of the cinchona amine catalyst, and rationalization of the absolute stereoselectivity by NMR spectroscopic studies and DFT calculations.
authors.affiliation: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1 D-45470, Mülheim an der Ruhr, Germany.
authors.forename: Olga
authors.initials: O
authors.lastname: Lifchits
authors.forename: Manuel
authors.initials: M
authors.lastname: Mahlau
authors.forename: Corinna M
authors.initials: CM
authors.lastname: Reisinger
authors.forename: Anna
authors.initials: A
authors.lastname: Lee
authors.forename: Christophe
authors.initials: C
authors.lastname: Farès
authors.forename: Iakov
authors.initials: I
authors.lastname: Polyak
authors.forename: Gopinadhanpillai
authors.initials: G
authors.lastname: Gopakumar
authors.forename: Walter
authors.initials: W
authors.lastname: Thiel
authors.forename: Benjamin
authors.initials: B
authors.lastname: List
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D002384:Catalysis; D002930:Cinchona Alkaloids / Q000737:chemistry*; D003500:Cyclization; D003512:Cyclohexanones / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006868:Hydrolysis; D007097:Imines / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D014269:Trifluoroacetic Acid / Q000737:chemistry
chemical_list: D000475:Alkenes; D000588:Amines; D002930:Cinchona Alkaloids; D003512:Cyclohexanones; D004852:Epoxy Compounds; D007097:Imines; D000644:Quaternary Ammonium Compounds; D006861:Hydrogen Peroxide; D014269:Trifluoroacetic Acid