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dc.contributor.authorFan, Huafang
dc.contributor.authorTong, Zongbo
dc.contributor.authorRen, Zhaoyang
dc.contributor.authorMishra, Kanchan
dc.contributor.authorMorita, Shunya
dc.contributor.authorEdouarzin, Edruce
dc.contributor.authorGorla, Lingaraju
dc.contributor.authorAverkiev, Boris
dc.contributor.authorDay, Victor W.
dc.contributor.authorHua, Duy H.
dc.date.accessioned2022-08-12T20:54:14Z
dc.date.available2022-08-12T20:54:14Z
dc.date.issued2022-05-05
dc.identifier.citationFan, H., Tong, Z., Ren, Z., Mishra, K., Morita, S., Edouarzin, E., Gorla, L., Averkiev, B., Day, V. W., & Hua, D. H. (2022). Synthesis and Characterization of Bimetallic Nanoclusters Stabilized by Chiral and Achiral Polyvinylpyrrolidinones. Catalytic C(sp3)-H Oxidation. The Journal of organic chemistry, 87(10), 6742–6759. https://doi.org/10.1021/acs.joc.2c00449en_US
dc.identifier.urihttp://hdl.handle.net/1808/33183
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.2c00449.en_US
dc.description.abstractSecond-generation chiral-substituted poly-N-vinylpyrrolidinones (CSPVPs) (−)-1R and (+)-1S were synthesized by free-radical polymerization of (3aR,6aR)- and (3aS,6aS)-5-ethenyl-tetrahydro-2,2-dimethyl-4H-1,3-dioxolo[4,5-c]pyrrol-4-one, respectively, using thermal and photochemical reactions. They were produced from respective d-isoascorbic acid and d-ribose. In addition, chiral polymer (−)-2 was also synthesized from the polymerization of (S)-3-(methoxymethoxy)-1-vinylpyrrolidin-2-one. Molecular weights of these chiral polymers were measured using HRMS, and the polymer chain tacticity was studied using 13C NMR spectroscopy. Chiral polymers (−)-1R, (+)-1S, and (−)-2 along with poly-N-vinylpyrrolidinone (PVP, MW 40K) were separately used in the stabilization of Cu/Au or Pd/Au nanoclusters. CD spectra of the bimetallic nanoclusters stabilized by (−)-1R and (+)-1S showed close to mirror-imaged CD absorption bands at wavelengths 200–300 nm, revealing that bimetallic nanoclusters’ chiroptical responses are derived from chiral polymer-encapsulated nanomaterials. Chemo-, regio-, and stereo-selectivity was found in the catalytic C–H group oxidation reactions of complex bioactive natural products, such as ambroxide, menthofuran, boldine, estrone, dehydroabietylamine, 9-allogibberic acid, and sclareolide, and substituted adamantane molecules, when catalyst Cu/Au (3:1) or Pd/Au (3:1) stabilized by CSPVPs or PVP and oxidant H2O2 or t-BuOOH were applied. Oxidation of (+)-boldine N-oxide 23 using NMO as an oxidant yielded 4,5-dehydroboldine 27, and oxidation of (−)-9-allogibberic acid yielded C6,15 lactone 47 and C6-ketone 48.en_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsCopyright © 2022 American Chemical Societyen_US
dc.subjectBimetalsen_US
dc.subjectMoleculesen_US
dc.subjectNanoclustersen_US
dc.subjectOxidationen_US
dc.subjectPolymersen_US
dc.titleSynthesis and Characterization of Bimetallic Nanoclusters Stabilized by Chiral and Achiral Polyvinylpyrrolidinones. Catalytic C(sp3)–H Oxidationen_US
dc.typeArticleen_US
kusw.kuauthorDay, Victor W.
kusw.kudepartmentChemistryen_US
dc.identifier.doi10.1021/acs.joc.2c00449en_US
dc.identifier.orcidhttps://orcid.org/0000-0001-7179-0108en_US
kusw.oaversionScholarly/refereed, author accepted manuscripten_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US
dc.identifier.pmidPMC35511477en_US
dc.rights.accessrightsembargoedAccessen_US


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