Regioselective oxygenative tetraamination of [60]fullerene. Fullerene-mediated reduction of molecular oxygen by amine via ground state single electron transfer in dimethyl sulfoxide

Hiroyuki Isobe, Takatsugu Tanaka, Waka Nakanishi, Loïc Lemiègre, Eiichi Nakamura

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    84 Citations (Scopus)

    Abstract

    The reaction of [60]fullerene with a variety of a secondary aliphatic amines in 20% v/v dimethyl sulfoxide in chlorobenzene under an atmospheric pressure of molecular oxygen allows regioselective introduction of four amino groups and one epoxide group around one pentagon of the fullerene molecule in good to high yield. This new synthesis of tetraaminofullerene expoxide can be carried out with a simple procedure on a multigram scale at room temperature and affords a variety of functionalized fullerene derivatives. Near-infrared analysis of a mixture of [60]fullerene and piperidine in a deaerated dimethyl sulfoxide/chlorobenzene mixture indicated equilibrium formation of [60]fullerene radical anion (C 60 .-) that persists at least for 2 weeks at room temperature but reacts immediately with molecular oxygen to give the tetraaminofullerene expoxide. The Benesi-Hildebrand analysis of the concentration dependency of the near-infrared absorption indicated that a [C 60 .- piperidine .+] radical ion pair is formed with an equivalent constant of K = 0.62 ± 0.02 M -1 at 25°C. This and other lines of evidence suggest that the oxygenative amination reaction involves C 60-mediated reduction of molecular oxygen by the amine.

    Original languageEnglish
    Pages (from-to)4826-4832
    Number of pages7
    JournalJournal of Organic Chemistry
    Volume70
    Issue number12
    DOIs
    Publication statusPublished - 2005 Jun 12

    ASJC Scopus subject areas

    • Organic Chemistry

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