One-step direct oxidation of fullerene-fused alkoxy ethers to ketones for evaporable fullerene derivatives
Open Access
- 21 May 2021
- journal article
- research article
- Published by Springer Science and Business Media LLC in Communications Chemistry
- Vol. 4 (1), 1-8
- https://doi.org/10.1038/s42004-021-00511-4
Abstract
Ketones are widely applied moieties in designing functional materials and are commonly obtained by oxidation of alcohols. However, when alcohols are protected/functionalized, the direct oxidation strategies are substantially curbed. Here we show a highly efficient copper bromide promoted one-step direct oxidation of benzylic ethers to ketones with the aid of a fullerene pendant. Mechanistic studies unveil that fullerene can serve as an electron pool proceeding the one-step oxidation of alkoxy group to ketone. In the absence of the fullerene pendant, the unreachable activation energy threshold hampers the direct oxidation of the alkoxy group. In the presence of the fullerene pendant, generated fullerene radical cation can activate the neighbour C–H bond of the alkoxy moiety, allowing a favourable energy barrier for initiating the direct oxidation. The produced fullerene-fused ketone possesses high thermal stability, affording the pin-hole free and amorphous electron-transport layer with a high electron-transport mobility.Keywords
Funding Information
- MEXT | Japan Society for the Promotion of Science (JP18H05329, JP20H00220, 20J13124)
- MEXT | JST | Core Research for Evolutional Science and Technology (JPMJCR20B5)
- MEXT | JST | Strategic International Collaborative Research Program (JPMJSC18H1)
This publication has 18 references indexed in Scilit:
- Efficient Regular Perovskite Solar Cells Based on Pristine [70]Fullerene as Electron‐Selective ContactChemSusChem, 2016
- Multifunctional Fullerene Derivative for Interface Engineering in Perovskite Solar CellsJournal of the American Chemical Society, 2015
- Kinetic Study of the Diels–Alder Reaction of Li+@C60 with Cyclohexadiene: Greatly Increased Reaction Rate by Encapsulated Li+Journal of the American Chemical Society, 2014
- FeCl3-Mediated Synthesis of Fullerenyl Esters as Low-LUMO Acceptors for Organic Photovoltaic DevicesOrganic Letters, 2012
- Indene−C60Bisadduct: A New Acceptor for High-Performance Polymer Solar CellsJournal of the American Chemical Society, 2010
- Selective Oxidation of Benzylic Alcohols and Ethers and Oxidative Cleavage of Benzylic Tetrahydropyranyl and Trimethylsilyl Ethers to Their Carbonyl Compounds by Dinitrogen Tetroxide–Impregnated Activated Charcoal (N2O4/Charcoal)Synthetic Communications, 2005
- Electrochemistry of Fullerenes and Their DerivativesAccounts of Chemical Research, 1998
- The Chemical Nature of Buckminsterfullerene (C 60 ) and the Characterization of a Platinum DerivativeScience, 1991
- Geminal interproton coupling constants in some methyl derivativesAustralian Journal of Chemistry, 1970
- The Activated Complex in Chemical ReactionsThe Journal of Chemical Physics, 1935