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Indication of Pd–C or Cu–C Intermediates in Bimetallic Nanoclusters During Pd/Au-PVP- or Cu/Au-PVP-Catalyzed Oxidations of endo-4-Oxatricyclo[5.2.1.02,6]-8-decene and Tetrahydro-γ-carbolines

Morita, Shunya
; 
Ren, Zhaoyang
; 
Gorla, Lingaraju
; 
Tong, Zongbo
; 
Edouarzin, Edruce
; 
Averkiev, Boris
; 
Day, Victor W.
; 
Hua, Duy H.
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Abstract
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.
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Date
2020-12-20
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Thieme Gruppe
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Chemistry Scholarly Works
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Bimetallic Cu/Au-PVP and Pd/Au-PVP nanoclusters, Catalytic C-H oxidation, Oxidative C-C bond formation
Citation
Morita, S., Ren, Z., Gorla, L., Tong, Z., Edouarzin, E., Averkiev, B., Day, V. W., & Hua, D. H. (2023). Indication of Pd-C or Cu-C Intermediate in Respective Bimetallic Nanoclusters Pd/Au-PVP or Cu/Au-PVP Catalyzed Oxidations of endo-4-Oxatricyclo[5.2.1.02,6]-8-decene and Tetrahydro-γ-carbolines. Synthesis, 55(8), 1227–1240. https://doi.org/10.1055/a-2001-6888
URI
https://hdl.handle.net/1808/34376
DOI
10.1055/a-2001-6888
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