Synthesis and Characterization of Bimetallic Nanoclusters Stabilized by Chiral and Achiral Polyvinylpyrrolidinones. Catalytic C(sp3)–H Oxidation

Abstract

Second-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.