title: Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions.
abstract: A new class of poly-N-vinylpyrrolidinones containing an asymmetric center at C5 of the pyrrolidinone ring were synthesized from l-amino acids. The polymers, particularly 17, were used to stabilize nanoclusters such as Pd/Au for the catalytic asymmetric oxidations of 1,3- and 1,2-cycloalkanediols and alkenes, and Cu/Au was used for C-H oxidation of cycloalkanes. It was found that the bulkier the C5 substituent in the pyrrolidinone ring, the greater the optical yields produced. Both oxidative kinetic resolution of (±)-1,3- and 1,2-trans-cycloalkanediols and desymmetrization of meso cis-diols took place with 0.15 mol % Pd/Au (3:1)-17 under oxygen atmosphere in water to give excellent chemical and optical yields of (S)-hydroxy ketones. Various alkenes were oxidized with 0.5 mol % Pd/Au (3:1)-17 under 30 psi of oxygen in water to give the dihydroxylated products in >93% ee. Oxidation of (R)-limonene at 25 °C occurred at the C-1,2-cyclic alkene function yielding (1S,2R,4R)-dihydroxylimonene 49 in 92% yield. Importantly, cycloalkanes were oxidized with 1 mol % Cu/Au (3:1)-17 and 30% H2O2in acetonitrile to afford chiral ketones in very good to excellent chemical and optical yields. Alkene function was not oxidized under the reaction conditions. Mechanisms were proposed for the oxidation reactions, and observed stereo- and regio-chemistry were summarized.
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Bo
authors.initials: B
authors.lastname: Hao
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Medha J
authors.initials: MJ
authors.lastname: Gunaratna
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Man
authors.initials: M
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Sahani
authors.initials: S
authors.lastname: Weerasekara
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Sarah N
authors.initials: SN
authors.lastname: Seiwald
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Vu T
authors.initials: VT
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Alex
authors.initials: A
authors.lastname: Meier
authors.affiliation: Department of Chemistry, Kansas State University , Manhattan, Kansas 66506, United States.
authors.forename: Duy H
authors.identifier: 0000-0001-7179-0108
authors.initials: DH
authors.lastname: Hua
mesh_terms: D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D053768:Metal Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D011760:Pyrrolidinones / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D011760:Pyrrolidinones