Catalytic oxidation of tricyclic endo-norbornene-fused tetrahydrofuran with the bimetallic nanocluster Cu/Au-PVP in the presence of H2O2 or t-BuOOH as the oxidant leads to C–H bond oxidation adjacent to the ether function to give 4-oxa-tricyclo[5.2.1.0]-8,9-exo-epoxydecane, however, oxidation with Pd/Au-PVP takes place at the C=C double bond to give the same epoxide and the oxidative three-bond forming dimeric product, dodecahydro-1,4:6,9-dimethanodibenzofurano[2,3-b:7,8-b′]bisoxolane. Formation of the latter product suggests the involvement of a reactive Pd–C intermediate. Similarly, oxidative C–C bond-forming reactions are observed in cycloaddition reactions of N2-Boc-1,2,3,4-tetrahydro-γ-carbolines and 2,3-dihydroxybenzoic acid with Cu/Au-PVP (2–5 mol%) and H2O2 at 25 °C, providing two-bond-forming [4+2] cycloadducts. Under similar reaction conditions, Pd/Au-PVP did not produce the corresponding cycloadduct, indicating a need for complexation between Cu and the carboxylic acid group of 2,3-dihydroxybenzoic acid and the allylic amine function of the γ-carbolines during the cyclization reaction. The reported intermolecular coupling reactions using Pd/Au-PVP or Cu/Au-PVP nanocluster catalysts under oxidative conditions at 25 °C are unprecedented.
Twin Proliferation and Prolongation under Kinetic Control: Pd–Au Janus Icosahedra versus Pd@Au Core–Shell Starfishes
- Award ID(s):
- 2105602
- NSF-PAR ID:
- 10421339
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 145
- Issue:
- 24
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- p. 13400-13410
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract
